CN101585525B - Preparation method of single-walled carbon nano-tube with adjustable diameter - Google Patents
Preparation method of single-walled carbon nano-tube with adjustable diameter Download PDFInfo
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- CN101585525B CN101585525B CN2008100115029A CN200810011502A CN101585525B CN 101585525 B CN101585525 B CN 101585525B CN 2008100115029 A CN2008100115029 A CN 2008100115029A CN 200810011502 A CN200810011502 A CN 200810011502A CN 101585525 B CN101585525 B CN 101585525B
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- walled carbon
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Abstract
The invention relates to a preparation technique of carbon nano-tubes, in particular to a preparation method of a single-walled carbon nano-tube with adjustable diameter, which is suitable to prepare the single-walled carbon nano-tube with adjustable diameter. The single-walled carbon nano-tube with adjustable diameter can be produced by adopting organic compound catalyst containing iron, cobalt or nickel with ultra high hydrogen flow and ultra low carbon source flow, and sulfur-containing growth promoter after the organic compound catalyst and the sulfur-containing growth promoter are uniformly mixed in a gas state and are input into a reaction region, wherein the mol ratio of hydrogen and carbon source is more than 300, and the mol ratio of sulfur and iron, cobalt or nickel is 1/100-1/5.The invention inhibits the scission reaction of hydrocarbon with ultra high flow by adopting large-flow hydrogen as buffer gas, and large-flow hydrogen etches the generated agraphitic carbon and mino r diameter single-walled carbon nano-tube, thereby improving the purity of the produced single-walled carbon nano-tube and narrowing the diameter.
Description
Technical field:
The present invention relates to the technology of preparing of CNT (carbon nano-tube), concrete a kind of for having the preparation method of the adjustable Single Walled Carbon Nanotube of diameter, be applicable to that preparation has the adjustable Single Walled Carbon Nanotube of diameter.
Background technology:
CNT (carbon nano-tube) be have one deck or multi-layer graphene according to certain helix angle curl form, diameter is the seamless tubular shaped structure of nanometer scale.CNT (carbon nano-tube) has the unique one dimension Nano structure and the performance of many excellences, and its subjects such as nanomaterial science, sub-of nano photoelectric, nanochemistry, microelectronics that are found to be have been opened up brand-new research field.The character of Single Walled Carbon Nanotube is decided by its diameter and chirality.
Through various countries scientist effort for many years,,, but still be faced with many difficulties and challenge as a large amount of preparations that can realize Single Walled Carbon Nanotube substantially and oriented growth etc. though obtained some achievements aspect preparing in Single Walled Carbon Nanotube.For example, the current Single Walled Carbon Nanotube of preparing is normally by the mixture of metallicity and semiconductive CNT (carbon nano-tube), and its diameter Distribution a wider range.If in preparation process, can realize the diameter and the chirality adjustability of carbon pipe, so not only can deepen understanding to its growth mechanism, bring new physical phenomenon, and will inevitably promote its application in the nanometer electronic device field.
The method of existing preparation Single Walled Carbon Nanotube mainly contains three kinds: hydrogen arc process, laser ablation method and chemical Vapor deposition process.Wherein, the hydrogen arc method is non-balanced reaction process, therefore product structure poor controllability, purity change greatly, because the measured response space is unfavorable for serialization and scale operation, and a large amount of graphite flakes that generated in this process are difficult for removing in aftertreatment, have influenced the mensuration and the application of Single Walled Carbon Nanotube intrinsic performance; Chemical Vapor deposition process can prepare Single Walled Carbon Nanotube in a large number continuously, but the diameter Distribution of the Single Walled Carbon Nanotube of preparing at present is still bigger, and its diameter and chirality adjustability are relatively poor, thereby influenced the application of Single Walled Carbon Nanotube aspect the high-performance nanometer electronic device.
Summary of the invention:
The object of the present invention is to provide the novel method of the adjustable Single Walled Carbon Nanotube of a kind of a large amount of preparation diameters, it is simple that this method has equipment, processing ease, energy consumption is low, therefore advantages such as product purity height, adjustability is high and it is continuous to be expected to, mass production can be used as a kind of Perfected process that is suitable for adjustable preparation.
Technical scheme of the present invention is:
The invention provides the preparation method of a kind of high purity, high quality, Single Walled Carbon Nanotube that diameter is adjustable, this method adopts Ultra-low carbon source flux, superelevation hydrogen flowing quantity, iron content (cobalt or nickel) organic compound catalyzer, contains growth promoter of sulfur, under gaseous state thorough mixing evenly after, import reaction zone then and generate the adjustable Single Walled Carbon Nanotube of diameter, wherein:
Iron content (cobalt or nickel) organic compound, as: ferrocene, dicyclopentadienylcobalt or nickelocene etc. are catalyzer, and its cold zone at 60-120 ℃ is slowly volatilized; Containing growth promoter of sulfur is sulphur powder or organic compounds containing sulfur, as: thiophene (C
4H
4S), dithiocarbonic anhydride (CS
2) or hydrogen sulfide (H
2S) etc.; Wherein, the mol ratio of sulphur and iron (cobalt or nickel) is 1/100-1/5, is preferably 1/50-1/20; The superelevation hydrogen flowing quantity is meant that adopting a kind of of big flow hydrogen or hydrogen and argon gas, nitrogen or several mixed gas is buffer gas, wherein the content of hydrogen is greater than 50at.%, the superelevation hydrogen flow rate is that 1.0-6.0cm/s (depresses at 1 standard atmosphere, as follows), in the preferred 1.3-4.6cm/s scope; The Ultra-low carbon source flux is meant and adopts ultralow flow methane, ethene, acetylene, alcohol, benzene or other small molecules hydrocarbon polymer as carbon source, and Ultra-low carbon source and course speed≤0.02cm/s is preferred≤0.01cm/s; Wherein, the mol ratio of hydrogen and carbon source is greater than 300.
Among the present invention, contain the 1/10-1/30 of growth promoter of sulfur and carbon source.
900 ℃-1350 ℃ of end reaction temperature (being preferably 1050 ℃-1250 ℃), soaking time 5-180min.
Used temperature rise rate be 10-60 ℃/min (be preferably 20-40 ℃/min).
Among the present invention, the diameter of the Single Walled Carbon Nanotube of acquisition can be regulated in the 1.3-2.2nm scope, and the purity of Single Walled Carbon Nanotube is 40-80wt%.
Characteristics of the present invention and beneficial effect are:
1. the present invention is by each reaction parameter of control, and the CNT (carbon nano-tube) that makes generation is the adjustable Single Walled Carbon Nanotube of diameter;
2. the present invention adopts big flow hydrogen to suppress the scission reaction of ultralow flow hydrocarbon polymer as buffer gas, decolorizing carbon and minor diameter Single Walled Carbon Nanotube that a large amount of simultaneously stream hydrogen etchings generate, thereby purity and its diameter that narrows of the Single Walled Carbon Nanotube that raising is produced;
The present invention at low temperatures, the metallocenes of slowly volatilizing catalyzer significantly reduces the content of metallic particles impurity in the Single Walled Carbon Nanotube that generates; Detailed process is as follows: after the hydrogen buffering gas of the carbon source of ultralow flow, gaseous sulfur and big flow mixes also preheating, import reaction zone together and scission reaction takes place, carbon atom is under the effect of iron (cobalt or nickel) catalyzer, thereon through process such as dissolving, diffusion and crystallization is separated out, the generation Single Walled Carbon Nanotube.If reaction conditions is suitable, then can generate the adjustable high quality Single Walled Carbon Nanotube of a series of diameters.
In a word, by the parameters such as volatilization temperature, hydrogen flowing quantity, carbon source flow and temperature of reaction of control metallocenes, realized that preparation has the adjustable Single Walled Carbon Nanotube of diameter.
Description of drawings:
Fig. 1. the transmission electron microscope photo of Single Walled Carbon Nanotube.
Fig. 2. the high resolution photo of Single Walled Carbon Nanotube.
Fig. 3. the Raman spectrum of the Single Walled Carbon Nanotube that a series of diameters are adjustable, wherein scheme the low frequency region that a is the Raman of Single Walled Carbon Nanotube, figure b is the high-frequency region of the Raman of carbon pipe.
Embodiment:
Embodiment 1
Carrier gas (buffer gas) hydrogen flow rate is 2.6cm/s, carbon source methane flow rate 0.005cm/s, and catalyzer is a ferrocene, containing growth promoter of sulfur is thiophene (C
4H
4S), the mol ratio of sulphur and iron is 1: 35, and the volatilization temperature of catalyzer is 120 ℃, and reaction zone temperature is 1100 ℃, and temperature rise rate is 20 ℃/min, insulation 5min.
Observe (Fig. 1) under the projection Electronic Speculum and show that product is very pure, foreign matter content is less; High power projection photo is observed and is shown that product is Single Walled Carbon Nanotube (Fig. 2); In the present embodiment, in the scope of 1.8 ± 0.2nm, Single Walled Carbon Nanotube purity is 40-80wt% to the Single Walled Carbon Nanotube diameter respectively.
Embodiment 2
Carrier gas is that hydrogen and argon gas mixed gas (mol ratio is 2: 1) flow velocity are 4.4cm/s, and the argon gas flow velocity is, carbon source methane flow rate 0.008cm/s, and catalyzer is a ferrocene, containing growth promoter of sulfur is thiophene (C
4H
4S), the mol ratio of sulphur and iron is 1: 35, and the volatilization temperature of catalyzer is 80 ℃, and reaction zone temperature is 1100 ℃, and temperature rise rate is 30 ℃/min, insulation 50min.
Observe under the Electronic Speculum and show that product is a Single Walled Carbon Nanotube; In the present embodiment, in the scope of 1.6 ± 0.2nm, Single Walled Carbon Nanotube purity is 40-80wt% to the Single Walled Carbon Nanotube diameter respectively.
Embodiment 3
Carrier gas gas velocity 3.2cm/s, carbon source ethene flow velocity 0.005cm/s, catalyzer is a nickelocene, containing growth promoter of sulfur is dithiocarbonic anhydride (CS
2), the mol ratio of sulphur and iron is 1: 15, and the volatilization temperature of catalyzer is 60 ℃, and reaction zone temperature is 1100 ℃, and temperature rise rate is 40 ℃/min, insulation 125min.
Observe under the Electronic Speculum and show that product is a Single Walled Carbon Nanotube; In the present embodiment, in the scope of 2.0 ± 0.2nm, Single Walled Carbon Nanotube purity is 40-80wt% to the Single Walled Carbon Nanotube diameter respectively.
Embodiment 4
Carrier gas gas velocity 1.32cm/s, carbon source ethene flow velocity 0.005cm/s, catalyzer is a dicyclopentadienylcobalt, containing growth promoter of sulfur is dithiocarbonic anhydride (CS
2), the mol ratio of sulphur and iron is 1: 35, and the volatilization temperature of catalyzer is 90 ℃, and reaction zone temperature is 1200 ℃, and temperature rise rate is 20 ℃/min, insulation 150min.
Observe under the Electronic Speculum and show that product is a Single Walled Carbon Nanotube; In the present embodiment, in the scope of 1.3 ± 0.2nm, Single Walled Carbon Nanotube purity is 40-80wt% to the Single Walled Carbon Nanotube diameter respectively.
Embodiment 5
Carrier gas gas velocity 2.6cm/s, carbon source acetylene flow velocity 0.005cm/s, catalyzer is a ferrocene, containing growth promoter of sulfur is hydrogen sulfide (H
2S), the mol ratio of sulphur and iron is 1: 35, and the volatilization temperature of catalyzer is 100 ℃, and reaction zone temperature is 1100 ℃, and temperature rise rate is 30 ℃/min, insulation 180min.Observe under the Electronic Speculum and show that product is a Single Walled Carbon Nanotube.
Observe under the Electronic Speculum and show that product is a Single Walled Carbon Nanotube; In the present embodiment, in the scope of 1.7 ± 0.2nm, Single Walled Carbon Nanotube purity is 40-80wt% to the Single Walled Carbon Nanotube diameter respectively.
Embodiment 6
Carrier gas gas velocity 3.3cm/s, carbon source acetylene flow velocity 0.002cm/s, catalyzer are dicyclopentadienylcobalt and nickelocene mixture (mass ratio of dicyclopentadienylcobalt and nickelocene is 1: 1), and containing growth promoter of sulfur is hydrogen sulfide (H
2S), the mol ratio of sulphur and iron is 1: 65, and the volatilization temperature of catalyzer is 70 ℃, and reaction zone temperature is 1100 ℃, and temperature rise rate is 40 ℃/min, insulation 50min.
Observe under the Electronic Speculum and show that product is a Single Walled Carbon Nanotube; In the present embodiment, in the scope of 2.2 ± 0.2nm, Single Walled Carbon Nanotube purity is 40-80wt% to the Single Walled Carbon Nanotube diameter respectively.
Embodiment 7
Carrier gas gas velocity 4.6cm/s, by the flow velocity 0.01cm/s of carbon source alcohol liquid level hydrogen, catalyzer is ferrocene and nickelocene mixture (mass ratio of ferrocene and nickelocene is 1: 1), containing growth promoter of sulfur is dithiocarbonic anhydride (CS
2), the mol ratio of sulphur and iron is 1: 40, and the volatilization temperature of catalyzer is 90 ℃, and reaction zone temperature is 1100 ℃, and temperature rise rate is 50 ℃/min, insulation 50min.
Observe under the Electronic Speculum and show that product is a Single Walled Carbon Nanotube; In the scope of 1.6 ± 0.2nm, Single Walled Carbon Nanotube purity is 40-80wt% to the Single Walled Carbon Nanotube diameter respectively.
Embodiment 8
Carrier gas is hydrogen and argon gas mixed gas (mol ratio 4: 1) flow velocity 2.6cm/s, flow velocity 0.009cm/s by carbon source alcohol liquid level hydrogen, ferrocene and dicyclopentadienylcobalt mixture (mass ratio of ferrocene and dicyclopentadienylcobalt is 1: 1), containing growth promoter of sulfur is dithiocarbonic anhydride (CS
2), the mol ratio of sulphur and iron is 1: 100, and the volatilization temperature of catalyzer is 90 ℃, and reaction zone temperature is 1050 ℃, and temperature rise rate is 10 ℃/min, insulation 80min.
Observe under the Electronic Speculum and show that product is a Single Walled Carbon Nanotube; In the scope of 1.9 ± 0.2nm, Single Walled Carbon Nanotube purity is 40-80wt% to the Single Walled Carbon Nanotube diameter respectively.
As shown in Figure 3, by the Raman spectrum of the adjustable Single Walled Carbon Nanotube of a series of diameters as seen, the diameter of Single Walled Carbon Nanotube and its breathing mould displacement at the low frequency region of Raman are inversely proportional to.
Claims (2)
1. the preparation method of the adjustable Single Walled Carbon Nanotube of a diameter, it is characterized in that: this method adopts superelevation hydrogen flowing quantity, Ultra-low carbon source flux, iron content, cobalt or nickel organic compound catalyzer, contains growth promoter of sulfur, under gaseous state thorough mixing evenly after, import reaction zone then and generate the adjustable Single Walled Carbon Nanotube of diameter; Wherein: the mol ratio of hydrogen and carbon source is greater than 300, and the mol ratio of sulphur and iron, cobalt or nickel is 1/100-1/5;
900 ℃-1350 ℃ of reaction zone temperatures, soaking time 5-180min;
Iron content, cobalt or nickel organic compound are ferrocene, dicyclopentadienylcobalt or nickelocene, and its cold zone at 60-120 ℃ is slowly volatilized;
Containing growth promoter of sulfur is sulphur powder, thiophene, dithiocarbonic anhydride or hydrogen sulfide;
The superelevation hydrogen flowing quantity is meant that adopting a kind of of big flow hydrogen or hydrogen and argon gas, nitrogen or several mixed gas is buffer gas, and wherein the content of hydrogen is depressed at 1 standard atmosphere greater than 50at.%, and the superelevation hydrogen flow rate is 1.0-6.0cm/s;
The Ultra-low carbon source flux is meant and adopts ultralow flow methane, ethene, acetylene, alcohol or benzene as carbon source that depress at 1 standard atmosphere, Ultra-low carbon source and course speed is≤0.02cm/s.
2. according to the preparation method of the adjustable Single Walled Carbon Nanotube of the described diameter of claim 1, it is characterized in that: the mol ratio that contains growth promoter of sulfur and carbon source is 1/10-1/30.
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| CN102320593B (en) * | 2011-08-30 | 2013-02-27 | 中国科学院金属研究所 | Controllable preparation method of high-oxidation-resistance high-purity single/double-wall carbon nanotube |
| CN103449405B (en) * | 2013-08-29 | 2015-06-24 | 中国科学院金属研究所 | Method for selectively growing metal-enriched single-wall carbon nanotube by using floating catalyst method |
| CN103466597B (en) * | 2013-09-02 | 2016-01-13 | 中国科学院金属研究所 | The method of a small amount of doped growing metallic single-wall carbon nano-tube of nitrogen on carbon grid |
| CN104005004B (en) * | 2014-05-16 | 2016-03-02 | 中国科学院金属研究所 | The growth method of a kind of minor diameter, metallic single-wall carbon nano-tube and application |
| JP6094723B1 (en) * | 2015-07-16 | 2017-03-15 | 東レ株式会社 | Method for producing carbon nanotube-containing composition |
| CN110357072B (en) * | 2019-07-10 | 2022-05-31 | 中国科学院金属研究所 | Macro and controllable preparation method of large-diameter and narrow-diameter distribution single-walled carbon nanotubes |
| CN114538416B (en) * | 2022-01-19 | 2023-06-02 | 北京大学 | Preparation method of carbon nano tube film |
| CN116281957B (en) * | 2023-04-04 | 2023-10-20 | 重庆中润新材料股份有限公司 | Preparation method of narrow-diameter distribution semiconductor single-walled carbon nanotube |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074471C (en) * | 1997-12-25 | 2001-11-07 | 中国科学院金属研究所 | Method for preparation openside nanometre carbon tube |
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| CN1074471C (en) * | 1997-12-25 | 2001-11-07 | 中国科学院金属研究所 | Method for preparation openside nanometre carbon tube |
Non-Patent Citations (1)
| Title |
|---|
| Y. Chen et al..Optimization of carbon nanotube powder growth using low pressure floating catalytic chemical vapor deposition.《Materials Chemistry and Physics》.2006,第98卷第2，4部分. * |
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