CN100427388C - Large-area ultra-thin carbon nanotube film and its preparation process - Google Patents
Large-area ultra-thin carbon nanotube film and its preparation process Download PDFInfo
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Abstract
The present invention relates to a large-area ultra-thin carbon nanotube film and preparation process thereof which belongs to the technical field of the synthesis and the application of carbon nano materials. The present invention discloses a large-area ultra-thin carbon nanotube film so that a carbon nanotube film having macroscopic dimension maintains an excellent characteristic of a microscopic carbon nanotube. The large-area ultra-thin carbon nanotube film is composed of a carbon nanotube, wherein the length of the carbon nanotube is a centimeter magnitude, and purity is larger than 90 wt percent. The minimum thickness of a single-layer carbon nanotube film can reach to 20 nm, colour approaches to transparent, and the area of the film is larger than 10cm<2>. The surface of the carbon nanotube is provided with a plurality of functional groups which have surface chemistry activity. The present invention also discloses the preparation process of the carbon nanotube film. The process further processes a carbon nanotube macroscopic body that the carbon nanotube macroscopic body is oxidated in air, and then, is soaked in dioxygen water; subsequently, strong acid is added, and then, the carbon nanotube macroscopic body is rinsed until rinsing solution forms neutrality; finally, alcohol or acetone drops in the aqueous solution of the carbon nanotube, so that the carbon nanotube floats out of water surface and unfolds to form the carbon nanotube film.
Description
Technical field
The invention belongs to the synthetic and applied technical field of carbon nanomaterial.
Background technology
Carbon nanotube is the monodimension nanometer material that is curled and form according to certain helix angle by one deck or multilayer graphite synusia.Owing to its unique geometry and electronic band structure have brought excellent electricity, optics, mechanics and thermal property.For example, the current capacity of carbon nanotube is up to 10
9A/cm
2Magnitude, high 1000 times than copper; Carbon nanotube can send cold light under photoinduction or electricity excite; Theoretical Calculation shows, the Young's modulus of carbon nanotube can be up to 1TPa, and being carried out macroscopical stretching experiment result, overlength Single Walled Carbon Nanotube rope shows, the tensile strength of Single Walled Carbon Nanotube long filament is up to 2.4GPa, Young's modulus reaches 77GPa, its specific tenacity is 2 times of high-strength carbon fibre, 56 times of steel, and specific modulus is steel and aluminium 7 times, 7.5 times of titanium; Theoretical Calculation shows that the capacity of heat transmission of carbon nanotube is up to 6600Wm
-1K
-1, be the highest in the known materials.Therefore can expect that carbon nanotube will be with a wide range of applications.
Common length of carbon nanotube is a micron dimension, is Powdered.People find when the performance of carbon nanotube and applied research, because carbon nanotube is difficult to disperse, poor continuity, and are difficult to give full play to its excellent performance characteristics.In actual applications, usually wish that carbon nanotube is macroscopical successive line, film or bulk, wish that perhaps carbon nanotube can disperse equably, therefore, the peacekeeping two dimension carbon nano-tube macroscopic body that acquisition has macro-size will bring great convenience to the applied research of carbon nanotube.
2002, the inventor adopted vertical floating catalytic cracking process successfully directly to synthesize Single Walled Carbon Nanotube long filament (Zhu HW, et al. that length reaches 40cm, Science 296,884～886,2002), this is the direct so far the longest and the strongest Single Walled Carbon Nanotube of synthetic.Subsequently, (the Jiang KL of Fan SS research group of Tsing-Hua University, et al., Nature 419,801,2002) and people (the Zhang M such as Zhang M of the upright university of Texas, USA, et al., Science 306,1358-1361,2004) from directional carbon nanotube array, extracted sub-thread and multiply multi-walled carbon nano-tubes rope respectively.People (Science 304 for LiYL, et al., 276-278,2004) such as the Li YL of Cambridge University adopt spinning technique directly to spin the multi-walled carbon nano-tubes rope from Reaktionsofen.Smalley RE research group of Rice Univ USA (Science 305 for Ericson LM, et al., 1447-1450,2004) adopts filtration method to extract the Single Walled Carbon Nanotube long filament that reaches several meters out.Although these carbon nanotube ropes that adopt spinning technique to extract have macro length, but, be that carbon nanotube by microcosmic length forms through the effect of Van der Waals power owing to its they, have very many defectives such as joint in the carbon nanotube rope, its performance than the carbon nanotube of microcosmic and directly the performance of synthetic with carbon nanotube of macro length obvious decline is arranged.But the macroscopic view that these carbon nanotube ropes are carbon nanotube is used and has been established solid foundation, and as behind these paper publishings, some media comments are said, the long rope of carbon nanotube can be made bullet-proof vest.But, so far as yet not relevant for the first-hand report of carbon nanotube bullet-proof vest.
The carbon nanotube rope can be spun into the carbon nanotube cloth of two dimension, because its excellent performance, expection can be applied in multiple occasion.It is carbon source that the inventor adopts organic solution, and ferrocene is a catalyzer, and sulphur is additive, has successfully synthesized length and has reached tens of centimetres double-walled carbon nano-tube macroscopic body, and this technology has obtained the national inventing patent (patent No.: ZL03143102.X).
People can obtain macroscopic carbon nanotube paper by filtering method.As the people such as Zhou Xiao (patent No.: ZL 03150052.8) of Tsing-Hua University by carbon nanotube dust being carried out a series of purifying and cuts short processing, then through filtering, obtain after the solution evaporation drying carbon nanotube paper.Specific embodiments is earlier carbon nanotube to be poured in the acid, continuous reflux, and ultrasonic then concussion, stirring, up to carbon nanotube fully being disperseed and removing impurity, dilute with water filters then, and it is standby to wash filter cake with water clean back; Carbon nanotube is dispersed in the water, ultrasonic agitation is dispersed in the water it again, forms even carbon nanotube dispersive solution; At last that carbon nano-tube solution is dry on carrier, form carbon nanotube paper.People (Endo M.et al. such as Endo M, Nature 433,476,2005) to adopt methane synthetic double-walled carbon nano-tube powder with the hydrochloric acid of 18wt% 100 ℃ of following reflow treatment 10 hours, oxidation 30 minutes in 500 ℃ air then is to remove amorphous carbon and support of the catalyst and the granules of catalyst in the sample.Double-walled carbon nano-tube after purifying is filtered on filtering membrane, just can obtain macroscopic, flexible good black carbon nanotube paper.By solution evaporation and filter type obtain carbon nanotube paper be by length be the carbon nanotube of micron number magnitude overlapped, be interwoven, its thickness reaches more than tens of microns, area can reach several square centimeters of magnitudes.But the performance of carbon nanotube paper is compared obvious reduction with macroscopical successive carbon nanotube, therefore is difficult to give full play to the excellent specific property of carbon nanotube itself.
Langmuir-Blogdett (LB) membrane technique obtains a proven technique of large-area unit molecule or multilayer film, and expanding the ultra-thin oil film of formation layer of even as oil droplet on the surface of water is exactly a kind of typical LB membrane technique.This technology is one of most effectual way that obtains at present film, but the LB membrane technique only limits to produce part organic polymer film at present.(Langmuir 17 for Sano M, et al., 5125-5128,2001 and for the report of having produced and characterized to some extent of the LB film of Single Walled Carbon Nanotube; Kim Y, et al., Synthetic Metals 135,747-748,2003; Guo YZ, et al., Physica B-CondensedMatter 323,235-236,2002), but these Single Walled Carbon Nanotube LB film be carbon nanotube dust is purified, cut short, disperse, prepare a series of processing such as chemical solution after, carbon nano-tube solution is dripped on matrixes such as silicon chip, behind the solution evaporation and the membranaceous carbon nanotube that obtains.Because carbon nanotube LB film is that mixed and disorderly accumulation of carbon nanotube of micron dimension forms by length, be difficult to form continuous thin film, a lot of local Single Walled Carbon Nanotube heaps that only comprise some islands on the microcosmic, thereby its performance can seriously descend.
Summary of the invention
In order to make the carbon nano-tube film with macro-size keep the characteristic of microcosmic carbon nanotube excellence, the present invention mainly solves following technical problem:
A) continuity of carbon nano-tube film and homogeneity.Although the carbon nanotube by micron dimension can synthesize certain thickness carbon nano-tube film through chemical treatment, but because in the carbon nano-tube film, there are a large amount of joints and defective, and, in film, causes carbon nanotube reunion because twining mutually, be that the carbon nanotube film uniformity is damaged, therefore its performance can't keep the performances such as electricity, mechanics of the excellence of microscopic dimensions carbon nanotube, and has limited its application.
B) the carbon nanotube film thickness is controlled, makes carbon nanotube thickness adjustable from several nanometers to tens micron even hundreds of micron as required, and particularly thickness is less than the carbon nano-tube film of 100nm.
C) obtain large-area carbon nano-tube film.The area of carbon current nanotube films is smaller, only is 2cm as people's synthetic carbon nano-tube film diameters such as Endo M, and thickness is then above 100 microns.
D) technological operation of preparation carbon nano-tube film is simple, environmental pollution is as far as possible little.
Technical scheme of the present invention is as follows:
In order to obtain large-area ultra-thin carbon nanotube film, at first synthetic dissimilar carbon nano-tube macroscopic body is comprising single wall, double-walled and multi-walled carbon nano-tubes.The inventor adopts floating catalytic cracking process controllably synthesizing single-wall, double-walled and multi-walled carbon nano-tubes macroscopic view.Its concrete processing step is:
With ferrocene and sulphur according to mol ratio 100: (1～30) uniform mixing is mixed with reaction soln as catalyst precursor according to the ratio that adds 5～100mg catalyst precursor in every milliliter of benzene, dimethylbenzene or the hexane solution;
Reaction chamber is heated to 900～1200 ℃, and the flow with 500～3000mL/min and 200～1000mL/min feeds rare gas element and hydrogen respectively;
Send the reaction soln of above-mentioned preparation to described reaction chamber with the speed of 0.05～0.5mL/min, the black carbon nanotube films that produces in the reaction zone of reaction chamber drifts out with air-flow, and is deposited on the rear end of reaction chamber.After reaction finished, the feed-disabling reaction soln stopped to feed hydrogen and reduces argon flow amount, and described reaction chamber is cooled to room temperature under the protection of rare gas element, can take out the carbon nano-tube macroscopic body of the black with certain viscosity from reaction chamber.
These carbon nano-tube macroscopic bodies are to be formed through self-assembly by the carbon nanotube that length reaches centimetre magnitude, so this carbon nano-tube film has good continuity.Obtain single wall, double-walled and multi-walled carbon nano-tubes, only need adjust a little and get final product the processing parameter of above-mentioned synthesizing carbon nanotubes.As want single-wall carbon nanotube synthesizing, and ferrocene and additive sulfur mol ratio need be reduced to 100: 1～100: 5, temperature of reaction is greater than 1000 ℃; Synthesize double-walled carbon nano-tube, then the mol ratio with ferrocene and additive sulfur was controlled at 100: 5～100: 15, and temperature of reaction is greater than 1000 ℃; And want the synthesizing multi-wall carbon nanotube, and then needing the mol ratio of ferrocene and sulphur was controlled at 100: 15～100: 30, temperature of reaction is greater than 900 ℃.
Owing to the carbon nano-tube macroscopic body that directly takes out from reaction chamber is overlapped and to tangle the group of formation cotton-shaped under the effect of air-flow by the multilayer carbon nanotube film, be difficult to directly separately, thereby can't directly obtain ultrafine, large-area, smooth carbon nano-tube film, therefore need further carry out follow-up processing.Concrete treatment step is:
1) earlier with the carbon nanotube that makes oxidation in 400～600 ℃ air 5～60 minutes, to remove part amorphous carbon particle.
2) to be immersed in concentration be in 10～30% the hydrogen peroxide to the carbon nanotube after will handling through step 1), soak time is 24～96 hours, further, the metal catalyst particles that is wrapped in the amorphous carbon is come out the amorphous carbon particulate oxidation in the carbon nano-tube film.
3) in step 2) add strong acid in the carbon nanotube after handling, example hydrochloric acid, sulfuric acid and nitric acid are with further removal amorphous carbon and granules of catalyst.Treatment effect was even more ideal when the concentration of experiment discovery strong acid was higher.
4) step 3) is handled carbon nanotube rinsing to the rinsing liquid that obtains and reach neutrality, the carbon nanotube after the processing still keeps the macroscopic membrane structure, but carbon nano-tube macroscopic body has not had viscosity in solution, and purity can be up to more than the 90wt%.
5) utilize the ultimate principle of LB film, in the aqueous solution of carbon nanotube, drip organic solutions such as alcohol or acetone, carbon nano-tube film emerges immediately, and launches rapidly under the effect of organic solution molecule, forms even, the smooth carbon nano-tube film of thickness of individual layer.Can adopt substrate (as silicon chip, tinsel, sheet glass etc.) or ring (as quartz ring, metal ring etc.) with the surface collection of carbon nano-tube film from the aqueous solution.
The carbon nano-tube film that adopts the method for the invention to prepare has following characteristics:
A) film mainly is made up of carbon nanotube, and its purity can be up to more than 90%, and the thickness of the ultra-thin carbon nanotube film of individual layer is can obtain the thinnest carbon nano-tube film so far between 20～100nm; This film is almost completely transparent, and this has tangible difference with the carbon nano-tube film that adopts additive method to obtain; Film thickness is controlled, by the thickness of control initial carbon nanotube films and the number of plies of controlling carbon nanotube film, can regulate and control the total thickness of carbon nano-tube film, and is adjustable in from tens nanometers to tens of micrometer ranges.
B) carbon nano-tube film is made up of for the carbon nano-tube bundle of centimetre magnitude length, has kept the excellent specific property of microcosmic carbon nanotube; The area of carbon nano-tube film is big, can surpass 10cm
2, be area maximum so far.
C) carbon nanotube is uniformly dispersed in film, does not reunite, but forms uniform reticulated structure, with carbon nanotube isolated island a large amount of in other carbon nanotube LB film obvious difference is arranged.
D) surface through the prepared carbon nano-tube film that goes out of this technology has multiple chemical functional group, therefore has good chemically reactive.The wetting ability of the carbon nano-tube film that the above-mentioned technology of process obtains can change by tensio-active agent.For not showing as super-hydrophobicity through the carbon nano-tube macroscopic body under the preparation attitude of any processing, the carbon nanotube that carbon nano-tube macroscopic body obtains after handling through subsequent step then shows tangible wetting ability, and hydrophilic, the hydrophobicity of carbon nano-tube film can change by adding organic solutions such as alcohol, acetone.
E) carbon nano-tube film can be collected on the multiple matrix, on matrixes such as glass, semiconductor silicon, quartz, metal, combines very firmly between carbon nano-tube film and the matrix, is difficult to separately.Also can collect and obtain independently carbon nano-tube film by ring.This has significant difference with the carbon nano-tube film that other modes of employing obtain.
The ultra-thin carbon nanotube film that adopts technology of the present invention to make has kept the good continuity of direct synthetic carbon nano-tube film, has therefore kept the performance of microcosmic carbon nanotube excellence.Up to 750MPa, (Science 304 for Li YL, et al., 276-278,2004 than the 116～460MPa height that adopts the spun multi-walled carbon nano-tubes rope of spinning system as the tensile strength of the double-walled carbon nano-tube film of individual layer; Zhang M, et al., Science 306,1358-1361,2004; Ericson LM, et al., Science 305,1447-1450,2004), also high 2 times (Nature 419,912 for Wang Y, et al., 2002) of the brilliant copper film of ratio nano; The electric property of this carbon nano-tube film is similar to single carbon nanotube electric property, and its room temperature resistivity only is 0.06m Ω cm, and is lower than the 0.7m Ω cm of Single Walled Carbon Nanotube long filament.Adopt the carbon nano-tube film of the large-area ultrathin that technology of the present invention makes itself to have very high intensity and favorable conductive, the capacity of heat transmission.The ultra-thin carbon nanotube film that the present invention makes can be used as filtering membrane, also can be used as electrode materials in ultracapacitor, solar-energy conversion systems, electrochemical synthesis or electrolytic process, is with a wide range of applications.
Embodiment
Further describe the present invention below by embodiment.
Example 1: with the double-walled carbon nano-tube film is example, and the employing spirituous solution is a spreading agent, collects with silicon chip, and concrete steps are:
1) taking by weighing the 0.25g mol ratio is that the mixture of 10: 1 ferrocene and sulphur is dissolved in 10 milliliters the xylene solution, is mixed with reaction soln.
2) temperature with horizontal reaction chamber is increased to 1150 ℃, feed the argon gas of 2000mL/min and the hydrogen of 400mL/min, reaction soln is sent in the reaction chamber with the speed of 0.1mL/min, the black carbon nanotube films that produces in the reaction zone of reaction chamber drifts out with air-flow, and is deposited on the rear end of reaction chamber.
3) after reaction finished, the feed-disabling reaction soln stopped to feed hydrogen and reduces argon flow amount, and reaction chamber is cooled to room temperature.
4) the double-walled carbon nano-tube macroscopic body of taking-up black from reaction chamber.
5) earlier with the oxidation 30 minutes in 450 ℃ air of direct synthetic double-walled carbon nano-tube macroscopic body.
6) to be immersed in concentration be that soak time is 72 hours in 10% the hydrogen peroxide to the carbon nanotube after will handling through step 5.After 36 hours, change 1 time 10% hydrogen peroxide at hydrogen peroxide dipping.
7) nitric acid of adding 70wt% in the carbon nanotube after step 6) is handled, the treatment time is 40 minutes.
8) carbon nanotube after the step 7) processing is extremely neutral with the distilled water rinsing.
9) in the aqueous solution of carbon nanotube, drip alcohol, carbon nano-tube film is emerged and expansion rapidly, form single thin film.
10) with silicon chip with the surface collection of carbon nano-tube film from water, can obtain to be deposited on double-walled carbon nano-tube film on the silicon substrate, large-area.
Fig. 1 has shown the photomacrograph of the ultra-thin carbon nanotube film that the employing quartz ring is collected.Arrow 1 indication is the double-walled carbon nano-tube film among Fig. 1, and arrow 2 indications are quartz ring.Ultra-thin carbon nanotube film is almost completely transparent as can be seen by contrasting.Under scanning electronic microscope and atomic force microscope, observe and show that the thickness of ultra-thin carbon nanotube film is between 30～100nm.Can ultra-thin carbon nanotube film intactly be taken out by substrates such as silicon chip, silica glass, tinsel or cavity ring.
Fig. 2 has shown the stereoscan photograph of ultra-thin carbon nanotube film, film is made up of very long carbon nano-tube bundle as can be seen, carbon nanotube is very pure, be evenly distributed, and hole is sparse between the carbon nanotube, adopt image analyzer to analyzing discovery at stereoscan photograph, the volume percent of carbon nanotube in film only is 25%.Carbon nanotube interweaves and forms the film of individual layer, can't be with carbon nano-tube film attenuate again, but can be with the thicker film of the overlapped formation of the film more than two or two.
Example 2: with the single-wall carbon nanotube membrane is example, and the employing acetone soln is a spreading agent, adopts quartz ring to collect, and concrete steps are:
1) taking by weighing the 0.05g mol ratio is that the mixture of 100: 5 ferrocene and sulphur is dissolved in 10 milliliters the hexane solution, is mixed with reaction soln.
2) temperature with horizontal reaction chamber is increased to 1200 ℃, feed the argon gas of 3000mL/min and the hydrogen of 1000mL/min, reaction soln is sent in the reaction chamber with the speed of 0.05mL/min, the black carbon nanotube films that produces in the reaction zone of reaction chamber drifts out with air-flow, and is deposited on the rear end of reaction chamber.
3) after reaction finished, the feed-disabling reaction soln stopped to feed hydrogen and reduces argon flow amount, and reaction chamber is cooled to room temperature.
4) the Single Walled Carbon Nanotube macroscopic body of taking-up black from reaction chamber.
5) earlier with the oxidation 5 minutes in 600 ℃ air of direct synthetic Single Walled Carbon Nanotube macroscopic body.
6) to be immersed in concentration be that soak time is 24 hours in 30% the hydrogen peroxide to the carbon nanotube after will handling through step 5).After 12 hours, change 1 time 30% hydrogen peroxide at hydrogen peroxide dipping.
7) hydrochloric acid of adding 37wt% in the carbon nanotube after step 6) is handled, the treatment time is 40 minutes.
8) carbon nanotube after the step 7) processing is extremely neutral with the distilled water rinsing.
9) in the aqueous solution of carbon nanotube, drip acetone, single-wall carbon nanotube membrane is emerged and expansion rapidly, form the single wall carbon nano-tube film of individual layer.
10) adopt quartz ring with the surface collection of single-wall carbon nanotube membrane from water, after it is taken out, obtain independently ultrafine single-wall carbon nanotube membrane, its area is relevant with the internal diameter of quartz ring.
Example 3: with the multi-wall carbon nano-tube film is example, and employing alcohol is spreading agent, collects with metallic matrix, and concrete steps are:
1) taking by weighing the 0.3g mol ratio is that the mixture of 10: 25 ferrocene and sulphur is dissolved in 10 milliliters the benzole soln, is mixed with reaction soln.
2) temperature with horizontal reaction chamber is increased to 900 ℃, feed the argon gas of 500mL/min and the hydrogen of 200mL/min, reaction soln is sent in the reaction chamber with the speed of 0.3mL/min, the black carbon nanotube films that produces in the reaction zone of reaction chamber drifts out with air-flow, and is deposited on the rear end of reaction chamber.
3) after reaction finished, the feed-disabling reaction soln stopped to feed hydrogen and reduces argon flow amount, and reaction chamber is cooled to room temperature.
4) from reaction chamber, take out the multi-walled carbon nano-tubes macroscopic body.
5) earlier with the oxidation 60 minutes in 400 ℃ air of direct synthetic multi-walled carbon nano-tubes macroscopic body.
6) to be immersed in concentration be that soak time is 96 hours in 20% the hydrogen peroxide to the multi-walled carbon nano-tubes after will handling through step 5).After 48 hours, change 1 time 20% hydrogen peroxide at hydrogen peroxide dipping.
7) sulfuric acid of adding 90wt% in the multi-walled carbon nano-tubes after step 6) is handled, the treatment time is 60 minutes.
8) the effective distilled water rinsing of multi-wall carbon nano-tube after the step 7) processing is extremely neutral.
9) in the aqueous solution of multi-walled carbon nano-tubes, drip spirituous solution, many walls of carbon nanotube films is emerged and expansion rapidly, form the multi-wall carbon nano-tube film of individual layer.
10) adopt stainless steel plate with the surface collection of multi-wall carbon nano-tube periosteum, obtain being deposited on the ultrafine multi-wall carbon nano-tube periosteum of stainless steel surface from water.
Claims (5)
1. large-area ultra-thin carbon nanotube film, it is characterized in that: described large-area ultra-thin carbon nanotube film by length for centimetre magnitude, purity is formed greater than single wall or the multi-walled carbon nano-tubes of 90wt%, carbon nanotube in the ultra-thin carbon nanotube film is uniformly dispersed, the carbon nano-tube film minimum thickness of individual layer reaches 20nm, color is near transparent, and the area of carbon nano-tube film is greater than 10cm
2Carbon nano tube surface in the described ultra-thin carbon nanotube film comprises multiple functional group, has chemical mobility of the surface.
2. the preparation technology of the described large-area ultra-thin carbon nanotube film of claim 1, the preorder processing step that comprises synthesizing single-wall or multi-walled carbon nano-tubes macroscopic body, it is characterized in that, the carbon nano-tube macroscopic body that the preorder processing step makes is further done following processing:
1) earlier with the oxidation 5～60 minutes in 400～600 ℃ air of the carbon nano-tube macroscopic body that makes;
2) to be immersed in concentration be that soak time is 24～96 hours in 10～30% the hydrogen peroxide to the carbon nanotube that above-mentioned processing is obtained;
3) carbon nanotube after handling through hydrogen peroxide adds strong acid;
4) rinse step 3) carbon nanotube to the rinsing liquid that obtains after handling is neutral;
5) in the aqueous solution of carbon nanotube, drip alcohol or acetone, carbon nano-tube film is emerged, launch to form even, the smooth carbon nano-tube film of thickness.
3. the preparation technology of large-area ultra-thin carbon nanotube film according to claim 2, it is characterized in that: described strong acid is hydrochloric acid, sulfuric acid or nitric acid.
4. the preparation technology of large-area ultra-thin carbon nanotube film according to claim 2 is characterized in that: adopt substrate or ring to collect the lip-deep ultra-thin carbon nanotube film of the aqueous solution.
5. the preparation technology of large-area ultra-thin carbon nanotube film according to claim 2, it is characterized in that: the concrete steps of the preorder technology of described synthesizing single-wall or multi-walled carbon nano-tubes macroscopic body are as follows:
With ferrocene and sulphur according to mol ratio 100: (1～30) uniform mixing is mixed with reaction soln as catalyst precursor according to the ratio that adds 5～100mg catalyst precursor in every milliliter of benzene, dimethylbenzene or the hexane solution;
Reaction chamber is heated to 900～1200 ℃, and the flow with 500～3000mL/min and 200～1000mL/min feeds rare gas element and hydrogen respectively;
Send the reaction soln of above-mentioned preparation to described reaction chamber with the speed of 0.05～0.5mL/min, the black carbon nanotube films that produces in the reaction zone of described reaction chamber drifts out with air-flow, and is deposited on the rear end of described reaction chamber; Reaction is cooled to room temperature with described reaction chamber after finishing under the protection of rare gas element, can take out the carbon nano-tube macroscopic body of black from described reaction chamber.
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