CN1170767C - Continuous synthesis process of single-wall carbon nanotube - Google Patents
Continuous synthesis process of single-wall carbon nanotube Download PDFInfo
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- CN1170767C CN1170767C CNB021374031A CN02137403A CN1170767C CN 1170767 C CN1170767 C CN 1170767C CN B021374031 A CNB021374031 A CN B021374031A CN 02137403 A CN02137403 A CN 02137403A CN 1170767 C CN1170767 C CN 1170767C
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- wall carbon
- ferrocene
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Abstract
The present invention relates to a continuous synthesis process of single-wall carbon nanotubes, which is characterized in that hydrogenous carrier gas continuously carries tetraethyl orthosilicate and ferrocene in a high-temperature reaction zone; the tetraethyl orthosilicate and the ferrocene are reacted in situ to generate nanometer composite particles of fe-silicon dioxide with catalytic effect; in a direct catalyzing atmosphere, carbon obtained by decomposing a raw material is formed into continuous single-wall carbon nanotubes; the temperature of the high-temperature reaction zone is within 900 to 1200 DEG C; carrier gas comprises hydrogen gas and diluent gas, wherein the mole percentage of the hydrogen gas is 5 to 85%; the duration time of the high temperature reaction zone is within 20 to 60 minutes, the total flow capacity of the hydrogenous carrier gas is 800 to 2400 ml/mil, the flow capacity of the tetraethyl orthosilicate is 20 to 100 mg/min, and the flow capacity of the ferrocene is 0.3 to 3 mg/min. The diameter of the single-wall carbon nanotubes is about 2 nm. The single-wall carbon nanotubes exist in a bundle form. The length of the single-wall carbon nanotubes is a plurality of microns to dozen of microns, and the yield is up to 8%.
Description
Technical field
The present invention relates to a kind of method of continuously synthesizing single-wall carbon nano tube, more specifically to a kind of with ferrocene and tetraethoxy method as the continuously synthetic high-quality Single Walled Carbon Nanotube in enormous quantities of raw material.
Background technology
From 1991 synthetic first obtain carbon nanotube since, because carbon nanotube especially Single Walled Carbon Nanotube has particular performances, receive concern especially as high strength, Chu Qing, electroconductibility, an electron emission and high-specific surface area etc., the huge purposes of potential is being arranged aspect advanced composite material, flat-panel monitor, fuel cell, lithium particle battery and the ultracapacitor.Though multi-walled carbon nano-tubes part begins to commercially produce, and also can't produce Single Walled Carbon Nanotube in enormous quantities up to now.At present the main synthetic method of Single Walled Carbon Nanotube has three kinds of arc plasma method, laser ablation method and catalysis thermal decomposition methods, wherein these two kinds of methods of arc process and laser method all need graphite is evaporated, consume lot of energy, be difficult to amplify technology as producing usefulness in enormous quantities.The catalysis thermal decomposition method is that catalyzer such as iron, cobalt, nickel are dispersed on pottery, silicon, graphite or the glass substrate, and by catalysis thermolysis carbon compound single-wall carbon nanotube synthesizing on substrate, the carbon compound of use is generally hydro carbons or carbon monoxide.But the resultant velocity of this method is very slow, and usually with the formation of multi-walled carbon nano-tubes, is difficult to be suitable for mass production.Find that afterwards nano-powder with some inorganicss is (as silicon-dioxide, aluminium sesquioxide, magnesium oxide etc.) as support of the catalyst, with transition metal (iron as catalyzer, cobalt, nickel, molybdenums etc.) preparation becomes nano-complex particle in advance, can obtain higher-quality Single Walled Carbon Nanotube [A.Peigney, Ch.Laurent, P.Dobigeon, et al.J.Mater.Res.12 (1997) 613.Jason H.Hafner, Michael J.Bronikowski, Bobak R.Azamian, et al.Chem.Phys.Lett.296 (1998) 195, Jing Kong, Alan M.Cassell, Hongjie Dai.Chem.Phys.Lett.292 (1998) 567, J.-F.Colomer, C.Stephan, S.Lefrant, et al.Chem.Phys.Lett.317 (2000) 83.].The common methods for preparing this nano-complex particle is that mineral powder is mixed with the nitrate solution of metal, then through super-dry, and calcining, reduction becomes the nano-complex particle of metal and inorganic carrier at last.This process need expends long time, and major cause is will grow up at the catalyzer of carrier surface to need the long time to suitable particle size, has influenced production efficiency.Use the improvement of fixed catalytic agent method as these, mobile catalysis method is that catalyst precursor such as ferrocene, pentacarbonyl-iron etc. are evaporated in the reactor, in gas phase, decompose and directly form metal catalyst particles, make the carbon source catalyse pyrolysis and form carbon nanotube, use ferrocene as catalyst precursor as Shenyang Inst. of Metals, Chinese Academy of Sciences, synthesized Single Walled Carbon Nanotube [H.M.Cheng, F.Li, G.Su, et al.Appl.Phys.Lett.72 (1998) 3282.].But this method needs higher relatively temperature, and the carbon source pyrolysis rate is too fast, is easy to form thicker carbon nanotube; Also collision mutually in air-flow of granules of catalyst simultaneously, the speed of growth is very fast, so only can generate the granules of catalyst of suitable dimension in narrow scope, relatively harsher to conditional request, experiment is repeatable poor.The research group of U.S. Rice University has developed with CO as carbon source, the pentacarbonyl-iron presoma as catalyzer, single-wall carbon nanotube synthesizing [pavelNikolaev under High Temperature High Pressure, Michael J.Bronikowski, R.Kelley Bradley, et al.Chem.Phys.Lett313 (1999) 91].But this method, and is carried out under the highly compressed condition as raw material with harmful carbon monoxide, will have a lot of problems in the mass production process.Therefore the method that does not up to the present also have a kind of comparatively ideal a large amount of single-wall carbon nanotube synthesizings.
Summary of the invention
The object of the present invention is to provide a kind of method of continuously synthesizing single-wall carbon nano tube, it is the form with the catalysis method that flows, in air-flow, directly form nano-complex particle, utilize the interaction of carrier and catalyzer, rapidly and efficiently synthetic high-quality Single Walled Carbon Nanotube.
The method of a kind of single-wall carbon nanotube synthesizing provided by the invention, it is characterized in that: with the presoma of ferrocene as catalyzer, with tetraethoxy as carbon source and silica source, directly in air-flow, to generate the composite nanoparticle of iron and silicon-dioxide as catalyzer, because the composite nanoparticle of iron and silicon-dioxide is the good catalyzer of Single Walled Carbon Nanotube, can generate a large amount of high-quality Single Walled Carbon Nanotube.Simultaneously because ferrocene and tetraethoxy all are continuous supplies, and the Single Walled Carbon Nanotube that generates can be collected in collector, so this method single-wall carbon nanotube synthesizing continuously.
Ferrocene that the present invention adopts and tetraethoxy are as catalyst precursor and carbon source, utilized the advantage separately of mobile catalysis method and carrier catalysis agent method fully: ferrocene steam is at high temperature separated out iron atom, form nano iron particles through collision, tetraethoxy has generated silicon-dioxide after decomposition, both form iron-silicon-dioxide composite nanometer particle by very fast direct interaction in air-flow, be very suitable for the growth of Single Walled Carbon Nanotube, thereby do not need the needed long complicated pre-treatment of carried catalyst described in the prior art report; Made full use of the advantage of silicon-dioxide, stoped the quick growth of iron particle in air-flow, can in the scope of broad, obtain high-quality product, the favorable repeatability of building-up process as carrier; The existence of Sauerstoffatom has hindered the deposition of carbon at the carbon tube-surface in the carbon source, even under than higher temperature, agraphitic carbon content is also very low, has avoided having in the common mobile catalysis method product shortcoming of a large amount of decolorizing carbon; And the growth velocity of Single Walled Carbon Nanotube is very fast under such high temperature, has just formed a large amount of Single Walled Carbon Nanotube at reactant gases during continuously apace by reaction tubes, has very high yield simultaneously.
System of the present invention can also directly add ethanol as additive carbon, increases the formation speed of carbon, thereby improves the output of Single Walled Carbon Nanotube.If increase the formation speed of carbon, then can cause rolling up of silica volume, the supplies consumption when bringing more the purification for subsequent disposal by improving the interpolation speed of tetraethoxy in atmosphere.Replace tetraethoxy can in the productivity that improves Single Walled Carbon Nanotube, reduce cost with a part of ethanol simultaneously as additive carbon.
Contain aerobic in the system of the present invention, after the thermolysis of high-temperature zone, can form a certain amount of water since itself can be in atmosphere water generation reaction, so insensitive to the oxygen and the water of the trace that carries in the unstripped gas.
Synthesizing in a horizontal quartz tube reactor of Single Walled Carbon Nanotube carried out as Fig. 1.At an internal diameter is earlier logical inert atmosphere (argon gas) or nitrogen in the crystal reaction tube about 150mm for 35mm length, be warmed up to 900 ℃-1200 ℃ of the temperature that set, the container that fills ferrocene is moved to the position of suitable temp, to control its vaporator rate.Successively bring tetraethoxy and ferrocene steam into high temperature reaction zone with hydrogenous carrier gas, obtain to have the iron-gold/silicon dioxide nano complex particle of catalytic effect through reaction in, the carbon that in direct catalysis atmosphere raw material is decomposed to obtain forms Single Walled Carbon Nanotube.The total flux of carrier gas is 800-2400ml/min, and the flow of tetraethoxy is 20-100mg/min, and ferrocene is 0.3-3mg/min.Carrier gas is mixed by hydrogen and diluent gas, and diluent gas is argon gas and nitrogen, perhaps their mixing, and wherein the shared molar percentage of hydrogen is 5-85%.The high temperature reaction zone time length was controlled at 20-60 minute, collected carbon nanotube in the exit with a screen cloth, and product is purified, weighed after the drying, with its structure of electron microscope observation, and measured its diameter.Purification process is to soak to carry out under the condition in 15-20 minute in 40% hydrofluoric acid aqueous solution.
The method of single-wall carbon nanotube synthesizing provided by the invention has with low cost, the yield height, and speed is fast, and equipment is simple, can continuous operation, be easy to be used for mass-produced characteristics.The diameter of resulting Single Walled Carbon Nanotube exists with the form of restrainting about 2nm, and length is several microns to tens of microns, and yield is up to 8%.
Description of drawings
Fig. 1 is the equipment configuration simplified schematic diagram.
Fig. 2 is the stereoscan photograph of purification after product.
Fig. 3 is the transmission electron microscope photo of product.
Among the figure:
1-hydrogen valve 2-inert gas valve 3-N
2Air valve 4-tetraethoxy
5-silica tube 6-ferrocene 7-stove 8-programmed temperature control instrument
9-porous-film 10-outlet 11-surge flask 12-whiteruss.
Embodiment
The present invention is further illustrated by embodiment below in conjunction with accompanying drawing:
Embodiment 1
Synthetic in horizontal quartz tube reactor shown in the accompanying drawing 1; under the situation that feeds argon shield; be warmed up to 1150 ℃; temperature rise rate is 15 ℃/min; feed then by carrier gas and carry the tetraethoxy that enters; wherein the flow of argon gas is 2000ml/min; the flow of hydrogen is 100ml/min, and the flow of tetraethoxy is 50mg/min, and the velocity of evaporation of ferrocene is 1.3mg/min; reaction continues 20 minutes; collect the about 54mg of product in the exit, wherein contain the about 45wt% of silicon-dioxide, product is put into 40% hydrofluoric acid aqueous solution soaked 15 minutes; clean oven dry then, obtain the Single Walled Carbon Nanotube of 25mg behind the purifying.With respect to the carbon in the tetraethoxy, yield is 5.4%.The electron scanning micrograph of resulting product as shown in Figure 2.The fascircular texture all formed of each root fiber wherein by many Single Walled Carbon Nanotube, as Fig. 3 is the transmission electron microscope photo of single fiber, as can be seen, fiber is the fascircular texture that Single Walled Carbon Nanotube forms, and diameter of single-wall carbon nano tube is about 2 nanometers in the tube bank.
Device is as accompanying drawing 1.Under nitrogen protection; speed with 10 ℃/min is warmed up to 900 ℃; feed then by carrier gas and carry the tetraethoxy that enters; wherein nitrogen flow is 800ml/min; hydrogen flowing quantity is 400ml/min; the flow of tetraethoxy is 35mg/min, and the ferrocene velocity of evaporation is 3mg/min, and duration of the reaction is 1 hour.It is membranaceous collecting the product that obtains in the exit, obtains the about 94mg of product.All the other are with embodiment 1.The product morphological structure also is similar to Fig. 2 and Fig. 3.
Embodiment 3
Device is as accompanying drawing 1.Under argon shield; speed with 15 ℃/min is warmed up to 1000 ℃; feed then by carrier gas and carry tetraethoxy and the ethanol that enters; wherein argon flow amount is 2000ml/min; hydrogen flowing quantity is 300ml/min, and the flow of tetraethoxy is 30mg/min, and the ethanol flow is 30mg/min; the steaming method speed of ferrocene is 3mg/min, and duration of the reaction is 30min.Collect the about 85mg of membranaceous product that obtains in the exit.All the other are with embodiment 1.The product morphological structure also is similar to Fig. 2 and Fig. 3.
Claims (4)
1. the method for a continuously synthesizing single-wall carbon nano tube, comprise with the ferrocene being the presoma of catalyzer, it is characterized in that bringing tetraethoxy and ferrocene into high temperature reaction zone continuously with hydrogenous carrier gas, generate the nano-complex particle of iron-silicon-dioxide through reaction in, in direct catalysis atmosphere, make raw material decompose the carbon that obtains and form single-wall continuous nanotube with catalytic effect; Described high temperature reaction zone temperature is 900-1200 ℃, and carrier gas is made up of hydrogen and diluent gas, and wherein the shared molar percentage of hydrogen is 5-85%; The time length of reaction zone is 20-60 minute; The total flux of described hydrogeneous carrier gas is 800-2400ml/mil, and the tetraethoxy flow is 20-100mg/min, and the flow of ferrocene is 0.3-3mg/min.
2. by the method for the described continuously synthesizing single-wall carbon nano tube of claim 1, it is characterized in that described diluent gas is argon gas or nitrogen or their mixing.
3. by the method for the described continuously synthesizing single-wall carbon nano tube of claim 1, it is characterized in that product that high temperature reaction zone is collected put into 40% HF aqueous solution soaking 15-20 minute, clean oven dry then.
4. by the method for the described continuously synthesizing single-wall carbon nano tube of claim 1, it is characterized in that partly substituting tetraethoxy as additive carbon with ethanol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101369473B (en) * | 2007-08-16 | 2011-12-07 | 同济大学 | Preparation of silicon carbide/silicon dioxide coaxial nanometer cable by floating catalysis method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100355649C (en) * | 2006-06-09 | 2007-12-19 | 清华大学 | Method of in-situ filling symbiotic iron nanometer wire on thin wall nanometer pipe |
| CN100391834C (en) * | 2006-09-22 | 2008-06-04 | 北京交通大学 | Preparation method of high-purity multi-wall carbon nano-tube |
| KR101543052B1 (en) * | 2008-03-07 | 2015-08-07 | 히타치가세이가부시끼가이샤 | Carbon nano-tube manufacturing method and carbon nano-tube manufacturing apparatus |
| US9987608B2 (en) | 2014-09-19 | 2018-06-05 | NanoSynthesis Plus, Ltd. | Methods and apparatuses for producing dispersed nanostructures |
| CN114604855A (en) * | 2022-03-14 | 2022-06-10 | 无锡东恒新能源科技有限公司 | Method for synthesizing single-walled carbon nanotubes based on atomic layer deposition catalysis |
| CN116374998A (en) * | 2023-04-20 | 2023-07-04 | 温州大学 | Preparation method for directly growing single-walled carbon nanotube horizontal array by using silicon oxide |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101369473B (en) * | 2007-08-16 | 2011-12-07 | 同济大学 | Preparation of silicon carbide/silicon dioxide coaxial nanometer cable by floating catalysis method |
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