CN1193931C - Synthesis of double walled carbon nano-tubes - Google Patents
Synthesis of double walled carbon nano-tubes Download PDFInfo
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- CN1193931C CN1193931C CN 03143102 CN03143102A CN1193931C CN 1193931 C CN1193931 C CN 1193931C CN 03143102 CN03143102 CN 03143102 CN 03143102 A CN03143102 A CN 03143102A CN 1193931 C CN1193931 C CN 1193931C
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- walled carbon
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Abstract
The present invention discloses a synthesis method of double walled carbon nanometer tubes which belongs to the range of a preparative technique of nanometer material. Hexane is used as a carbon source, ferrocene is used as a catalyst front body, the mixed gas of argon and hydrogen gas is used as carrier gas, and sulfur is used as additive. The double walled carbon nanometer tubes are synthesized on a horizontal resistance furnace by a chemical vapo (u) r deposition method. The sulfur is directly used for replacing thiophene, which can guarantee that the sulfuric concentration of solution is stable in a reaction process. The mixed gas with large flow capacity of the argon and the hydrogen gas is used for obtaining the double walled carbon nanometer tubes. The present invention is simple, has high stability, and is suitable for synthesizing the double walled carbon nanometer tubes in batch.
Description
Technical field
The invention belongs to the nano material preparation technical scope, particularly a kind of synthetic method of double-walled carbon nano-tube.
Background technology
Carbon nanotube has excellent physicals and mechanical property, has very application prospects.Double-walled carbon nano-tube (double-walled carbon nanotubes) is the key types between Single Walled Carbon Nanotube (single-walledcarbon nanotubes) and the multi-walled carbon nano-tubes (multi-walled carbon nanotubes).The layer of double-walled carbon nano-tube is 0.34～0.42nm with the spacing of layer, and the interlamellar spacing of general multi-walled carbon nano-tubes is big.Because the bigger interlamellar spacing structure of double-walled carbon nano-tube, double-walled carbon nano-tube have similar to Single Walled Carbon Nanotube even superior physical properties more.In addition, because big diameter and the interlamellar spacing of double-walled carbon nano-tube can be used as excellent hydrogen storage material.Right research helps disclosing carbon nano tube growth mechanism to double-walled carbon nano-tube.At present, research is a focus in nano materials research field to the double-walled carbon nano-tube synthetic.
The method of at present synthetic double-walled carbon nano-tube mainly contains arc discharge method (arc-discharge) and chemical Vapor deposition process (Chemical Vapor Deposition).Preparation technology's more complicated of arc discharge method is to having relatively high expectations of equipment.Used chemical Vapor deposition process is to adopt hydrocarbon gas (CH at present
4Perhaps C
2H
2) as carbon source, because used gas flow very low (＜20 ml/min), the double-walled carbon nano-tube output for preparing is very low, and contains a large amount of catalyzer and amorphous carbon particle in the product, these impurity have had a strong impact on the performance of double-walled carbon nano-tube.People such as the Ci Lijie of Inst. of Physics, CAS are report in " Chemical PhysicsLetters, 2002,359:63～67 ": to using C
2H
2Prepare double-walled carbon nano-tube as carbon source and study, the result shows that sulphur plays an important role to the formation of double-walled carbon nano-tube, but their output and also has a large amount of catalyzer and amorphous carbon particle in milligram magnitude per hour in product.The method of seeking the synthetic double-walled carbon nano-tube of a kind of suitable batch will be the key of double-walled carbon nano-tube performance and applied research.
The Zhu Hongwei of machinery system of Tsing-Hua University reaches report in " Carbon; 2002; 40:2021～2025 " at " Science; 2002; 296:884～886 ": adopt hexane solution as carbon source, ferrocene is as catalyst precursor, and thiophene is as additive, hydrogen has synthesized overlength Single Walled Carbon Nanotube rope as carrier gas in vertical resistance furnace.Change processing parameter simultaneously, also can obtain double-walled carbon nano-tube sometimes.But under his processing parameter, the output of single wall and double-walled carbon nano-tube is all very low, usually less than 5wt%.
Adopting hydrocarbon organic solution is to produce the common method of directed multi-walled carbon nano-tubes as carbon source.The parameter of producing directed multi-walled carbon nano-tubes is: 120mg ferrocene/10mL benzene, the concentration of thiophene are 0.4wt%, and temperature of reaction is 600～850 ℃, and hydrogen and hydrogen flowing quantity are respectively 900mL/min and 150mL/min, and the amount of feed of solution is 0.4mL/min.The diameter of the directed multi-walled carbon nano-tubes of being produced is thick (generally more than 30 nanometers), although can obtain very a spot of Single Walled Carbon Nanotube under appropriate condition.But,, in the middle of product, do not find the existence of double-walled carbon nano-tube because processing parameter is improper.Present technique is improved original method, to be suitable for the growth of double-walled carbon nano-tube.Temperature of reaction is brought up to more than 1150 ℃ to help the growth of double-walled carbon nano-tube, increased catalyst concentration to form more forming core core, the concentration that increases sulphur is with the growth of the carbon nanotube that helps minor diameter.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of double-walled carbon nano-tube, it is characterized in that: be carbon source with the normal hexane, ferrocene is a catalyst precursor, the mixed gas of argon gas and hydrogen is carrier gas, sulphur is as additive, with chemical Vapor deposition process synthetic double-walled carbon nano-tube on horizontal electric resistance furnace, its synthesis technique is: with ferrocene and sulphur according to 20: 1～5: 1 uniform mixing of mol ratio as catalyst precursor, be dissolved in the hexane solution according to the ratio that adds 15～50 milligrams of catalyzer in every ml n-hexane, temperature of reaction is 1100～1180 ℃, the flow of argon gas and hydrogen is respectively 1～2.5 liter/minute and 0.3～0.6 liter/minute, the rate of feed of solution is 0.2～0.5 ml/min, reaction times is to close hydrogen after 30～60 minutes and reduce argon flow amount, with the electric furnace cool to room temperature, can collect in the rear end of silica tube mainly by double-walled carbon nano-tube form membranaceous, cotton-shaped black product.
The invention has the beneficial effects as follows that 1. adopt normal hexane as the output of carbon source with the raising product, directly adopt sulphur to replace thiophene, the concentration that can guarantee sulphur in the solution is more stable in reaction process, and the argon gas of the big flow of employing and hydrogen gas mixture are to obtain double-walled carbon nano-tube.2. present technique is simple to operate, and stability is higher, is suitable in batches synthetic double-walled carbon nano-tube.
Description of drawings
Fig. 1 is the height explanation transmission electron microscope photo of double-walled carbon nano-tube bundle.
Embodiment
The present invention is a kind of synthetic method of double-walled carbon nano-tube.Be to carry out in the silica tube in horizontal silica tube resistance furnace experimental installation.Respectively according to following technology: mol ratio be 5: 1,10: 1,20: 1, ratio take by weighing an amount of ferrocene and sulphur, mix the back and in mortar, grind and made catalyst precursor with uniform mixing in 30 minutes.300 milligrams, 400 milligrams, the 1000 milligrams catalyst precursors that prepare are dissolved in 20 milliliters the normal hexane, are mixed with reaction soln.Temperature of reaction is elevated to 1100 ℃, 1150 ℃, 1180 ℃, feed 1 liter/minute, 1.5 liters/minute, 2 liters/minute argon gas and 0.3 liter/minute, 0.4 liter/minute, 0.6 liter/minute hydrogen, the speed of reaction soln with 0.3 ml/min is sent in the silica tube with peristaltic pump, react and close hydrogen and reduce argon flow amount after 30 minutes, 40 minutes, 50 minutes, with the electric furnace cool to room temperature.Can collect membranaceous, the cotton-shaped black product of about 2 grams in the rear end of silica tube, these black products mainly are made up of double-walled carbon nano-tube.Wherein double-walled carbon nano-tube accounts for 60% (weight percent) of product.Detection by equipment such as scanning electronic microscope, transmission electron microscopes finds that the diameter of double-walled carbon nano-tube is 1.5～2.5 nanometers, and wherein diameter is being dominant of 2 nanometers.The double-walled carbon nano-tube for preparing with the organic solution normal hexane with use C
2H
2The form and the structural similitude (as shown in Figure 1) of the double-walled carbon nano-tube for preparing as carbon source.
Claims (1)
1. the synthetic method of a double-walled carbon nano-tube, it is characterized in that: be carbon source with the normal hexane, ferrocene is a catalyst precursor, the mixed gas of argon gas and hydrogen is carrier gas, sulphur is as additive, with chemical Vapor deposition process synthetic double-walled carbon nano-tube on horizontal electric resistance furnace, its synthesis technique is: with ferrocene and sulphur according to 20: 1～5: 1 uniform mixing of mol ratio as catalyst precursor, be dissolved in the hexane solution according to the ratio that adds 15～50 milligrams of catalyzer in every ml n-hexane, temperature of reaction is 1180 ℃, the flow of argon gas and hydrogen is respectively 1～2.5 liter/minute and 0.3～0.6 liter/minute, the rate of feed of solution is 0.2～0.5 ml/min, reaction times is to close hydrogen after 30～60 minutes and reduce argon flow amount, with the electric furnace cool to room temperature, can collect in the rear end of silica tube mainly by double-walled carbon nano-tube form membranaceous, cotton-shaped black product.
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| CN 03143102 CN1193931C (en) | 2003-06-09 | 2003-06-09 | Synthesis of double walled carbon nano-tubes |
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| CN 03143102 CN1193931C (en) | 2003-06-09 | 2003-06-09 | Synthesis of double walled carbon nano-tubes |
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| CN1193931C true CN1193931C (en) | 2005-03-23 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302986C (en) * | 2004-05-10 | 2007-03-07 | 华东理工大学 | Method for preparing Nano carbon tubes |
| CN100337908C (en) * | 2004-08-31 | 2007-09-19 | 中国科学院金属研究所 | Method for preparing two-wall nanocarbon tube with low cost |
| KR100657913B1 (en) * | 2004-11-20 | 2006-12-14 | 삼성전자주식회사 | method of synthesizing single-wall carbon nanotube at room temperature and atmosphere pressure |
| CN100387516C (en) * | 2005-11-10 | 2008-05-14 | 上海交通大学 | Method for direct and continuous preparing supershort carbon nanometer tube |
| CN100404736C (en) * | 2006-01-10 | 2008-07-23 | 华东理工大学 | Process for preparing plate type nano carbon fibre |
| CN100391834C (en) * | 2006-09-22 | 2008-06-04 | 北京交通大学 | Preparation method of high-purity multi-wall carbon nano-tube |
| CN100443404C (en) * | 2007-02-14 | 2008-12-17 | 天津大学 | Method for preparing carbon nano tube including Ethylenediamine double-injection |
| CN101830455B (en) * | 2010-04-30 | 2012-07-04 | 北京航空航天大学 | Method for synthesizing continuous carbon nanometer tube film |
| CN101941692B (en) * | 2010-09-21 | 2012-05-23 | 上海大学 | Preparation method of high-crystallinity double-walled carbon nano tube |
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2003
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