CN101454242A - Method for preparing single walled carbon nanotubes from a metal layer - Google Patents

Method for preparing single walled carbon nanotubes from a metal layer Download PDF

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CN101454242A
CN101454242A CNA2007800194147A CN200780019414A CN101454242A CN 101454242 A CN101454242 A CN 101454242A CN A2007800194147 A CNA2007800194147 A CN A2007800194147A CN 200780019414 A CN200780019414 A CN 200780019414A CN 101454242 A CN101454242 A CN 101454242A
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soccerballene
metal level
diameter
single walled
carbon source
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CN101454242B (en
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H·坦南特
H·张
J·马
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Hyperion Catalysis International Inc
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0009—Forming specific nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/152—Fullerenes
    • C01B32/156—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/159—Carbon nanotubes single-walled
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/02—Single-walled nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/36—Diameter

Abstract

Methods of preparing single walled carbon nanotubes are provided. An arrangement comprising one or more layers of fullerene in contact with one side of a metal layer and a solid carbon source in contact with the other side of metal layer is prepared. The fullerene/metal layer/solid carbon source arrangement is then heated to a temperature below where the fullerenes sublime. Single walled carbon nanotubes are grown on the fullerene side of the metal layer.

Description

The method for preparing Single Walled Carbon Nanotube from metal level
The application requires the U.S.S.N.60/743 of submission on March 29th, 2006,927 rights and interests and right of priority, and its content is attached to herein by reference at this.The application still is the part continuation application of the PCT/US2006/012001 that submitted on March 29th, 2006, PCT/US2006/012001 requires the U.S.S.N.60/665 of submission on March 29th, 2005,996 rights and interests and right of priority, both contents all are attached to herein by reference at this.
Background of invention
Invention field
The present invention relates to prepare the method for Single Walled Carbon Nanotube.More particularly, the present invention relates to prepare from metal level the method for Single Walled Carbon Nanotube, described metal level one side contacts with soccerballene and opposite side contacts with solid-state carbon source.Perhaps, replace solid-state carbon source, metal level can be saturated or can contact with non-solid-state carbon source with carbon atom.
Carbon nanotube
The invention belongs to carbon nanotube (having another name called protofibril) field.Carbon nanotube be diameter less than 1.0 μ, preferably less than 0.5 μ, even be more preferably less than the vermiform carbon deposits of 0.2 μ.Carbon nanotube can be many walls (that is, having more than in the graphite linings on the nanometer tubular axis) or single wall (that is, only having a graphite linings on the nanometer tubular axis).The known carbon nanotube that also has other types is as herringbone protofibril (for example, similar nested taper) etc.During generation, the form of carbon nanotube can be discrete nanotube, nanotube aggregate (that is the fine and close microcosmic particle structure that, comprises the carbon nanotube that tangles or tie up) or both mixtures.
Carbon nanotube is different with the commercially available continuous carbon fibre that gets.For example, the diameter of continuous carbon fibre (all the time greater than 1.0 μ and be generally 5-7 μ) is much larger than the diameter (usually less than 1.0 μ) of carbon nanotube.Carbon nanotube also has intensity and the electric conductivity that is much better than carbon fiber.
Carbon nanotube is also different with carbon black with other forms of carbon such as standard graphite on physics and chemical property.Standard graphite is because its structure and can be through oxidated until almost completely saturated.In addition, carbon black have graphene-structured for being the usually decolorizing carbon of spheroidal particle form of (as carbon-coating round unordered nuclear).On the other hand, carbon nanotube has one or more basically around the orderly Graphene carbon atomic layer of nanotube cylinders axle concentric arrangement.These differences especially make and are difficult to predict carbon nanotube chemical with graphite and carbon black.
Multi-walled carbon nano-tubes and Single Walled Carbon Nanotube differ from one another.For example, multi-walled carbon nano-tubes has a plurality of graphite linings along the nanometer tubular axis, and Single Walled Carbon Nanotube only has a graphite linings on the nanometer tubular axis.
The method that produces multi-walled carbon nano-tubes also is different from order to produce the method for Single Walled Carbon Nanotube.Specifically, obtain many walls or Single Walled Carbon Nanotube, need the various combination of catalyzer, support of the catalyst, starting material and reaction conditions.Some combination also can obtain the mixture of multi-walled carbon nano-tubes and Single Walled Carbon Nanotube.
The method that forms multi-walled carbon nano-tubes is well known.For example, Baker and Harris, Chemistry and Physics of Carbon, Walker and Thrower compile, the Vol.14197883 page or leaf; Rodriguez, N., J.Mater.Research.Vol.8,3233 pages (1993); Oberlin, A. and Endo, M., J.of Crystal Growth.Vol.32 (1976), the 335-349 page or leaf; No. the 4th, 663,230, the United States Patent (USP) of Tennent etc.; No. the 5th, 171,560, the United States Patent (USP) of Tennent etc.; Iijima, Nature 354, 56,1991; Weaver, Science 265, 1994; De Heer, Walt A., " Nanotubes and the Pursuit of Applications (nanotube and application are sought), " MRS Bulletin, in April, 2004; Deng.All these reference all are attached to herein by reference at this.
The method of making Single Walled Carbon Nanotube is also known for everyone.For example, " Single-shellcarbon nanotubes of 1-nm diameter (the monoshell carbon nanotube of 1-nm diameter) ", SIijima and T Ichihashi Nature, vol.363,603 pages (1993); " Cobalt-catalysedgrowth of carbon nanotubes with single-atomic-layer walls (the cobalt catalytic growth with carbon nanotube of monoatomic layer wall); " D S Bethune, C H Kiang, M SDeVries, G Gorman, R Savoy and R Beyers Nature, vol.363,605 pages (1993); No. the 5th, 424,054, the United States Patent (USP) of Bethune; Guo, T., Nikoleev, P., Thess, A., Colbert, D.T. and Smalley, R.E., Chem.Phys.Lett.243:1-12 (1995); Thess, A., Lee, R., Nikolaev, P., Dai, H., Petit, P., Robert, J., Xu, C, Lee, Y.H., Kim, S.G., Rinzler, A.G., Colbert, D.T., Scuseria, G.E., Tonarek, D., Fischer, J.E. and Smalley, R.E., Science, 273:483-487 (1996); Dai., H., Rinzler, A.G., Nikolaev, P., Thess, A., Colbert, D.T. and Smalley, R.E., Chem.Phys.Lett.260:471-475 (1996); No. the 6th, 761,870, the United States Patent (USP) of Smalley etc. (also being WO 00/26138); " Controlled production ofsingle-wall carbon nanotubes by catalytic decomposition of CO onbimetallic Co-Mo catalysts (carrying out the control production of Single Walled Carbon Nanotube), " by the catalytic deposition of CO on bimetal Co-Mo catalyzer Chemical Physics Letters, 317 (2000) 497-503; Maruyama etc., " Low-temperature synthesis ofhigh-purity single walled carbon nanotubes from alcohol (low temperature that is carried out the high purity Single Walled Carbon Nanotube by alcohol is synthetic), " Chemical Physics Letters, 360, the 229-234 pages or leaves (on July 10th, 2002); No. the 6th, 333,016, the United States Patent (USP) of Resasco etc.; R.E.Morjan etc., Applied Physics A, 78,253-261 (2004), etc.All these reference all are attached to herein by reference at this.
In addition, Maruyama, S., " Morphology and chemical state of Co-Mocatalysts for growth of single-walled carbon nanotubes vertically alignedon quartz substrates (being used to be grown in the Co-Mo catalyst form and the chemical state of vertically aligned Single Walled Carbon Nanotube on the quartz substrate); " Journal of Catalysis, 225, the 230-239 pages or leaves (2004) describe a kind of under vacuum on flat surfaces the method for growing single-wall nanotube woods.The bimetallic catalyst that comprises Co and Mo precursor is deposited on the quartz surfaces, and then calcination and reduction are to form the metallic particles that high-density is piled up.Single Walled Carbon Nanotube from these metallic particles growths shows 1 * 10 17/ m 2Density and about 5 microns length.K.Hata, " Water-assisted highly efficient synthesis of impurity-freesingle-walled carbon nanotubes (water of Single Walled Carbon Nanotube free from foreign meter is auxiliary efficient synthetic); " Science, 306, the 1362-1364 pages or leaves (2004) are described the another kind of water assisted CVD method that makes from the technology that is coated with the Si wafer growing single-wall carbon nano tube woods of iron thin film.The catalytic activity that they observe water stimulates strengthens and causes and highly reach 2.5 millimeters super densification (10 14-10 15/ m 2) and the extensive growth of vertically aligned nanotube woods.All these reference all are attached to herein by reference at this.
Other currently known methodss comprise WO 2006/130150, " Functionalized SingleWalled Carbon Nanotubes (functionalized Single Walled Carbon Nanotube) " and United States Patent (USP) the 6th, 221, No. 330, " Process For Producing Single Wall Nanotubes UsingUnsupported Metal Catalysts And Single Wall Nanotubes ProducedAccording To This Method (with the method for unsupported Catalyst Production single-walled nanotube and the single-walled nanotube that produces according to this method) ".In addition, at Maruyama etc., " Synthesisof single-walled carbon nanotubes with narrow diameter-distribution fromfullerene (having a Single Walled Carbon Nanotube that narrow diameter distributes), " by soccerballene is synthetic Chem. Phys.Lett., in 375, the 553-559 pages or leaves (2003) report use alcohol as carbon source at low relatively temperature 550-800 ℃ of following growing single-wall carbon nano tube for example.Find those so diameter Distribution very wide (0.8-1.3nm) and homogeneity is very poor and become with temperature of the single-walled nanotube of growth.When soccerballene directly was used as carbon source, the author found that diameter Distribution has certain improvement, is 0.8-1.1nm, but still indeterminate according to the Raman spectrum homogeneity.All these reference all are attached to herein by reference at this.
Yet present known Single Walled Carbon Nanotube method inclination is in the Single Walled Carbon Nanotube size that is extensively distributed.The diameter measurement of Single Walled Carbon Nanotube uses Raman spectrum to carry out usually.Use and be equipped with wavelength and collect Raman excitation as the typical Raman spectrometer of the continuous helium-neon laser of 632.8nm.At about 1580cm -1Under Raman peaks be present in pyrolytic graphite (HOPG), pyrolytic graphite and the charcoal of all types of graphite samples such as high orientation.This peak is commonly referred to as " G-band ".When material in the Graphene plane or when the graphite crystal edge comprises defective, have 1355cm -1The peak.This band is commonly referred to as " D-band " and has shown that the position of this band depends on laser excitation wavelength strongly." the radially breathing pattern (RBM) " that observe single-walled nanotube (is usually less than 300cm -1), wherein all carbon atoms all experience equal radial displacement.The trickle change of laser excitation frequency produces resonance Raman(RR)effect.Research about RBM has shown that itself and SWCNT diameter are inversely proportional to.This relation is represented with following equation:
ω RBM＝(223.75/d)cm -1
ω wherein RBMBe the RBM frequency, d is SWCNT diameter (in a nanometer).For measuring indivedual nanotubes, this relation is different slightly.Bandow etc., " Effect of the growthtemperature on the diameter distribution and chirality of single-wallcarbon nanotubes (growth temperature is to the influence of diameter of single-wall carbon nano tube distribution and chirality), " Physical Review Letters,80, the 3779-3782 pages or leaves (1998); Jishi etc., " Phononmodes in carbon nanotubes (the Phonon pattern of carbon nanotube), " Chemical Physics Letters, 209, the 77-82 pages or leaves (1993).All these reference all are attached to herein by reference at this.
In above-mentioned equation and run through this specification sheets, the diameter of nanotube is defined as the distance between the carbon nuclei at pipe diameter two ends.Should be appreciated that this diameter is different from the distance with the nearest approach of second nanotube, the latter is because bigger by the repulsion of the corresponding π cloud of TEM definition usually.
Table A provides as before at Jorio, A etc., " Structural (n; m) Determination ofIsolated Single-Wall Carbon Nanotubes by Resonant RamanScattering (structure of carrying out isolating Single Walled Carbon Nanotube by resonance Raman scattering is determined (n; m)), " Physical Review Letters, The American Physical Society, Vol.86, No.6, the sample diameter and the ω that are reported among the Table I of 1118-21 page or leaf (February 5 calendar year 2001) and the II RBMDependency, described document is attached to herein by reference:
Table A
(n，m) d t[nm] Θ [degree] ω RBM(calculated value) [cm -1] ω RBM(experimental value) [cm -1]
(18，6) 1.72 13.9 144.4 144(2)
(19，4) 1.69 9.4 146.8 ...
(20，2) 1.67 4.7 148.3 ...
(21，0) 1.67 0.0 148.8 148(5)
(15，9) 1.67 21.8 148.8 ...
(12，12) 1.65 30.0 150.3 151(3)
(16，7) 1.62 17.3 153.0 154(5)
(17，5) 1.59 12.5 156.4 156(6)
(13，10) 1.59 25.7 156.4 156(1)
(18，3) 1.56 7.6 158.8 158(1)
(19，1) 1.55 2.5 160.0 160(3)
(14，8) 1.53 21.1 162.0 ...
(11，11) 1.51 30.0 164.0 164(1)
(15，6) 1.49 16.1 166.7 165(1)
(16，4) 1.46 10.9 170.4 169(1)
(17，2) 1.44 5.5 172.7 174(1)
(18，0) 1.43 0.0 173.5 176(1)
(14，1) 1.15 3.4 215.1 210(1)
(10，6) 1.11 21.8 223.1 ...
(9，7) 1.10 25.9 224.9 ...
(11，4) 1.07 14.9 232.2 229(1)
(10，5) 1.05 19.1 236.1 237(2)
(12，2) 1.04 7.6 238.2 ...
(8，7) 1.03 27.8 240.3 239(2)
(11，3) 1.01 11.7 244.7 ...
The quantity of using along with the compounding technology of carbon nanotube increases, and needs to produce Single Walled Carbon Nanotube with narrow dimension more or diameter Distribution improvement method with the more accurate application that allows Single Walled Carbon Nanotube.
Summary of the invention
The invention provides from comprising metal level, preparing the novel method of Single Walled Carbon Nanotube with the soccerballene and the device of the solid-state carbon source that contacts with described metal level opposite side of described metal level one side contacts.After preparing soccerballene/metal level/solid carbon source component, be heated and be lower than the temperature that makes the distillation of described soccerballene.Solid-state carbon source and soccerballene are partly dissolved on the metal level interface at least and make Single Walled Carbon Nanotube long at the soccerballene adnation of metal level.After having the nanotube of nucleation, soccerballene temperature can be raise so that Single Walled Carbon Nanotube is grown to a greater degree (for example, 700-1100 ℃).
In an exemplary, can use the soccerballene (for example, C60, C70, C100, C36 etc.) of any kind.Soccerballene can being deposited upon on the metal level with one or more close packed array.
In an exemplary, metal level can comprise the metal catalyst that makes the Single Walled Carbon Nanotube growth, as Fe, Co, Mn, Ni, Cu and Mo.Metal layer thickness preferably makes carbon be diffused into metal level opposite side (for example, 1-20nm, 2-20nm, 3-5nm etc.) from the solid-state carbon source of metal level one side.
In an exemplary, solid-state carbon source can be carbon fiber or any other solid-state carbon source known in the art.
In another exemplary, Single Walled Carbon Nanotube is used as is prepared with the metal level that soccerballene contacts with non-solid-state carbon source certainly about the described similar approach of metal level that contacts with solid-state carbon source.
In another exemplary, Single Walled Carbon Nanotube is used as contacting with soccerballene certainly about the described similar approach of metal level that contacts with solid-state carbon source and preparing with the saturated metal level of carbon atom.
Method growing single-wall carbon nano tube of the present invention is trooped (multiplicity), in wherein said the trooping within diameter D ± 5% of the Single Walled Carbon Nanotube of the diameter of at least 80% described Single Walled Carbon Nanotube in being present in described trooping.Diameter D can be in the 0.6-2.2nm scope.
The accompanying drawing summary
Fig. 1 is the graphic extension according to the soccerballene/metal level of an exemplary of the present invention/solid carbon source apparatus.
Fig. 2 is the graphic extension that an exemplary soccerballene according to the present invention dissolves and Single Walled Carbon Nanotube begins to grow.
Fig. 3 is the graphic extension according to exemplary Single Walled Carbon Nanotube growth of the present invention.
Fig. 4 A and Fig. 4 B are the SEM Photomicrograph of carbon nanotubes grown on the catalyzer of C60/Fe/ carbon interlayer structure.
Fig. 5 A and Fig. 5 B are the transmitted electron micro image from the CNT of interlayer catalyzer growth.
Detailed description of preferred embodiments
The invention provides the novel method that a kind of device from soccerballene, metal level and solid-state carbon source prepares Single Walled Carbon Nanotube.In this assembly, metal level forms or is seated on the solid-state carbon source surface, metal level one side is contacted and by solid-state carbon source load with solid-state carbon source.The opposite side of metal level is put or deposited to soccerballene.Thereby, we can say that metal level one side contacts with soccerballene and opposite side contacts with solid-state carbon source.The assembling of this device can any order be carried out.
Assemble soccerballene/metal level/solid carbon source apparatus or interlayer, it just is heated in inert atmosphere is lower than the temperature that (for example within 10 ℃ or within 5 ℃) make the distillation of described soccerballene.Should understand this and be dynamic system: soccerballene is vaporized simultaneously and is dissolved in the metal level.Therefore, " apparent " sublimation temperature (for example, being about 650 ℃ for the C60 soccerballene under barometric point) is best measures by the thermogravimetric analysis of actual interlayer.
Suitable temperature range can be about 500 ℃-700 ℃ under barometric point, this depends on employed soccerballene.If growth step under high pressure carries out, can run into higher soccerballene sublimation temperature.Think that pressure change can cause the equilibrium partial pressure of soccerballene in gas phase to change, therefore influence vaporization motivating force.In any case, under said temperature, soccerballene and solid-state carbon source can be dissolved in the metal level, surpass the thermodynamic activity of carbon in the Single Walled Carbon Nanotube up to the thermodynamic activity of institute's dissolved carbon.Specifically, think that the partly soluble soccerballene in this stage and metal layer contacting can have nucleogenesis or promote the Single Walled Carbon Nanotube growth, because the thermodynamic activity of the carbon in the Single Walled Carbon Nanotube wall is than the thermodynamic activity low (for example, more stable) of carbon in soccerballene that heats or the solid-state carbon source.In addition, as hereinafter illustrated, partly soluble soccerballene will compatibly serve as the end cap of the Single Walled Carbon Nanotube with same diameter, therefore good " crystal seed " of growing for Single Walled Carbon Nanotube.
Yet, it should be noted that Single Walled Carbon Nanotube can have the diameter different with the soccerballene end cap of original " as crystal seed ".In the present invention, soccerballene or also can serve as nucleation accelerating agent.That is to say that soccerballene is used for promoting Single Walled Carbon Nanotube nucleation and growth.Therefore, a branch of Single Walled Carbon Nanotube with homogeneous diameter of 1.6nm can be produced by the 0.7nm soccerballene under certain condition.The promoter action of soccerballene can self-growing Single Walled Carbon Nanotube narrow diameter distribute and confirm.This makes the Raman spectrum of described product present unimodal usually in the RBM zone but not shows some different diameter groups' multiple signal.
After causing the Single Walled Carbon Nanotube growth, can introduce gaseous carbon source.The available gaseous carbon source is CO, hydrocarbon and alcohol.Should understand and introduce gaseous carbon source in principle and can make process of growth infinitely carry out, and not be subjected to solid-state carbon source quantity limitation.Continuous processing is therefore practical.
Because partly soluble soccerballene provides the initial nucleation site of Single Walled Carbon Nanotube, so the growth pattern of Single Walled Carbon Nanotube can be influenced by the arrangement of soccerballene on metal level.For example, if soccerballene is arranged on the layer on surface of metal with the close-packed layer, then Single Walled Carbon Nanotube can closely packed quasicrystal rope or Shu Shengchang so that the metal-carbon interface stabilityization.Single Walled Carbon Nanotube since carbon be dissolved into metal level one side and be diffused into the metal level opposite side and continued growth and become the nucleation pipe from solid-state carbon source.
As before illustrated, initial reaction temperature should be lower than the temperature that makes soccerballene distillation so that soccerballene for example is partially dissolved in hemisphere or the half-spherical construction, therefore described hemisphere or half-spherical construction will be the suitable end cap of Single Walled Carbon Nanotube, serve as " crystal seed " (or as crystal seed to promote growth) of Single Walled Carbon Nanotube growth.Yet,, no longer need to keep this inferior sublimation temperature as long as Single Walled Carbon Nanotube has begun growth (for example, having finished the crystal seed setting).The temperature of reaction that can raise is to obtain higher or growth velocity (for example, prolong or elongation nanotube itself) faster.Preferred higher temperature is about 700 ℃-1100 ℃.Make the Single Walled Carbon Nanotube continued growth, want up to obtaining or useful length.
Three kinds of compositions are described separately hereinafter in further detail.Also can use other starting material.
Soccerballene
Soccerballene is the well-known technical term of industrial use and approval, is meant usually only to be made up of to produce the roughly carbon form of spherical (for example, " buckyball (buckyball) ") the carbon atom that is bonded together.Thereby the soccerballene of normal use has 60 carbon and is called as the C60 soccerballene.According to the present invention, also can use the soccerballene that comprises greater or less than any other form of 60 carbon atoms, as C70, C100, C36 etc.
Soccerballene has almost spherical shape (" spherical ").As one man, the end of Single Walled Carbon Nanotube is the hemisphere form usually.Thereby half dissolved soccerballene (being similar to hemisphere) will become the suitable end cap of the Single Walled Carbon Nanotube with same diameter.Therefore, partly soluble soccerballene will become good " crystal seed " to promote the Single Walled Carbon Nanotube growth, because its semi-spherical shape is consistent with the semi-spherical shape of Single Walled Carbon Nanotube end because of its semisphere character.Thereby carbon nanotube bundles can be from a plurality of soccerballene nucleation and growth.
In addition, as the crystal seed or the initial nucleation source of Single Walled Carbon Nanotube growth, can utilize the size of the size control Single Walled Carbon Nanotube of soccerballene.For example, the technician who manages to obtain dominant large-size Single Walled Carbon Nanotube will use the C100 soccerballene to replace less C36 soccerballene, because the diameter of C100 soccerballene is bigger.
Under this same principle, use soccerballene also to control the dimension/diameter distribution or the variation of Single Walled Carbon Nanotube largely as crystal seed or nucleation site.For example, compare, use the C60 soccerballene will produce the narrower distribution/variation of Single Walled Carbon Nanotube dimension/diameter fully with other methods of not controlling initial nucleation site or seed sized.
Metal level
Soccerballene is placed on the metal level that helps the growth of promotion Single Walled Carbon Nanotube.In preferred embodiments, soccerballene is placed on the metal level, and does not tentatively contact with any possible source of pollution.The currently known methods of realizing this task comprises sputter and atomic deposition.Can use other common methods.The soccerballene number of plies on the metal level preferably is enough to make metal level saturated substantially.
In preferred embodiments, metal level comprises the metal catalyst of Single Walled Carbon Nanotube growth.For example, metal level can comprise the metal that is selected from Fe, Co, Mn, Ni, Cu and Mo.But can use the metal of other catalysis Single Walled Carbon Nanotube equally.
Metal level can be forms such as film, coating, thin slice, film.Preferred metal layers is formed evenly and its surface smoothing.Metal layer thickness should make dissolved carbon be diffused into the metal level opposite side from the carbon Solid State Source (hereinafter discussing) of metal level one side.Metal layer thickness can be about 1nm to 20nm, is preferably about 2nm to 10nm, or more preferably about 3nm is to 5nm.
Different metal can cause the different thickness limitation, and this depends on its carbon dissolution and mass transfer character.For example, iron is preferred metal because its carbon dissolution high and make carbon atom from metal level one side more effectively mass transfer to opposite side.
Solid-state carbon source
In soccerballene opposite and metal level one side contacts is solid-state carbon source.Solid-state carbon source provides the carbon atom supply that makes the Single Walled Carbon Nanotube growth.Specifically, solid-state carbon source is dissolved in the metal level and is diffused into the metal level opposite side, becomes the part of the Single Walled Carbon Nanotube of growth.
In preferred embodiments, solid-state carbon source does not have the space or does not have the space substantially, the space can along with carbon dissolution in metal and be interrupted or distortion nanocarbon/metal interface.Solid-state carbon source does not also preferably contain non-carbon heteroatoms or does not contain non-carbon heteroatoms substantially, and non-carbon heteroatoms can be separated the gas of metal level and solid-state carbon source with metal level reaction so that its passivation or formation.If there is heteroatoms, preferably it does not participate in carbon nano tube growth.For example, hydrogen will be preferred heteroatoms, because it is dissolved in the metal level, diffuse through metal level, leave metal/carbon nanotube interface with the hydrogen form subsequently.Preferably the solid-state carbon source surface with metallic contact should have high rim/basal plane carbon ratio so that the metallic film stabilization.
There are many solid-state carbon sources to can be used among the present invention.For example, if vitreous carbon does not have greying to be lower than the degree of the thermodynamic activity of Single Walled Carbon Nanotube to its thermodynamic activity, then it is a suitable carbon source.Pure carbon pitch also is the solid-state carbon source that suits as the pure carbon pitch that makes by pyrolysis polycyclic aromatic hydrocarbon, and is like this equally by the crosslinked carbon resin that cyclotrimerization or oxidative coupling diacetylene-benzene make.Also can use the needle-like crystal of the polyparaphenylene that makes by anodic oxidation benzene.
The commercially available carbon fiber that gets is preferred carbon source.Comparing with the carbon fiber based on PAN, is preferred based on the bituminous carbon fiber.The most useful carbon fiber is for having the carbon fiber at graphene layer as much as possible edge on fiber surface.This can measure by SEM.The vapor phase growth carbon nanofiber also is useful carbon source as Pyrograf I and Pyrograf III that derives from Applied Sciences Corp. or the VGCF that derives from Showa Denka Corp..
Other embodiments
Replace using solid-state carbon source, can use non-solid-state carbon source such as gaseous state or liquid carbon source to substitute solid carbon the carbon atom supply that makes the Single Walled Carbon Nanotube growth is provided.In this embodiment, non-solid-state carbon source is not necessarily limited to soccerballene opposite side and metal layer contacting.Required satisfied condition just is that non-solid carbon source is diffused in the metal level and/or passes metal level, becomes the part of the Single Walled Carbon Nanotube of growth.The example of possible gaseous carbon source comprises hydrocarbon, CO and alcohol.
In another exemplary, the Single Walled Carbon Nanotube saturated metal level of the carbon atom growth of can using by oneself.Can use the carbon source (for example, solid-state, liquid, gaseous state) of any currently known methods and physics attitude to make metal level saturated, because importantly supply carbon atom in this embodiment so that the Single Walled Carbon Nanotube growth.
The gained Single Walled Carbon Nanotube
Method growing single-wall carbon nano tube of the present invention is trooped, and wherein the diameter of at least 80% described Single Walled Carbon Nanotube is being present within diameter D ± 5% of the Single Walled Carbon Nanotube in trooping in described trooping.In other words, diameter D represents to be present in the diameter of the specific Single Walled Carbon Nanotube in trooping, thereby the diameter of the residue Single Walled Carbon Nanotube of (preferred 80-90%, more preferably 80-95%, even more preferably 80-99%) is within D ± 5% in described trooping at least 80%.Diameter D can use raman spectroscopy measurement, preferably in the 0.6-2.2nm scope, and 1.0-1.8nm more preferably, even 1.2-1.6nm more preferably.
Embodiment
The details of some embodiments of the present invention have been set forth so that thorough of the present invention is provided.It will be apparent to those skilled in the art that and to use other embodiments and can change without departing from the present invention.In addition, for simplicity promote to understand purpose of the present invention, omitted or refining the well-known feature that can provide by the state of the art in affiliated field.
Following examples further specify various feature of the present invention, and are not intended to limit by any way the scope of the present invention that is limited by accessory claim.
Embodiment 1
Prepare solid-state carbon source by the polymkeric substance carbonization
Solid-state carbon source at first prepares via the polymkeric substance carbonization.Comprise 10-30% polymkeric substance such as PAM-3k, resol, polyvinyl chloride and bituminous solution by the polymer dissolution of respective amount is prepared in suitable solvent such as water, alcohol, ketone, ester etc.Subsequently the platinum line is immersed in the described solution, be formed on the metal wire surface at evaporating solvent post polymerization thing tectum.The thickness estimation of formed polymer covering is 1-3mm.After drying is finished, the Pt line that applies is put installation (mounted) in the metal evaporator MEM-010 inside of being made by Balzers Union Ltd..By making electric current pass through the Pt line, owing to the resistance of Pt line is heated and makes the polymkeric substance carbonization.This process is monitored by vacuum pressure, does not have pressure to increase until recording.
Embodiment 2
The catalyst precursor of preparation sandwich structure
In metal evaporator MEM-010 inside, the tungsten line is installed on the electrode and with some iron or cobalt line (purity is greater than 99.99%) around the tungsten coil of wire around, as the thermal evaporation source metal.The thickness of metal cladding is by quartzy steady arm monitoring.The carbon that makes in embodiment 1 applies and produces thickness on the Pt line surface is Fe or the Co metal cladding of 0.5-5nm.At last, (purity derives from BuckyUSA greater than 99.9%, Inc) is placed in the stainless steel sift boat, and described stainless steel sift boat further ties up on the tungsten line so that the evaporation soccerballene with soccerballene.Apply the C that forms 5-10nm on the platinum line in metal/carbon subsequently 60Tectum is to form the catalyst precursor C of sandwich structure on the platinum line 60/ [Fe or Co]/solid carbon.
Embodiment 3
Use carbon fiber to prepare the catalyst precursor of sandwich structure
Use identical method and equipment and make the catalyzer of sandwich structure, wherein use International by Tech Trade, the asphalt-based carbon fiber that Inc makes as solid carbon to substitute the solid carbon that derives from as embodiment 2 described polymkeric substance carbonizations.Preparation of Catalyst is C 60/ [Fe or Co]/carbon fiber.
Embodiment 4
Catalyst precursor by sandwich structure is made nanotube
The catalyzer that makes in embodiment 1,2 and 3 heated via resistive heating and in metal evaporator inside under vacuum via current control at 500-1000 ℃.The multi-walled carbon nano-tubes that diameter is 6-10nm is checked and observed to treated sample by SEM (Fig. 4 A and 4B) and TEM (Fig. 5 A and 5B).
Embodiment 5
The catalyst precursor of preparation sandwich structure on smooth ground
The description that is similar to embodiment 1-3 prepares the catalyst precursor of sandwich structure.At first the resol emulsion is deposited on the silicon wafer via dip-coating.Subsequently, in argon gas, heat the sample that applies down and form solid carbon with carbonized polymers at 1000-1200 ℃.After carbon forms, the Si wafer placement that applies is deposited on metal such as Fe, Co, Ni or Cu on the wafer surface in metal evaporator (for example MED-010) and via physical vapor deposition.The thickness of metal cladding is by quartzy steady arm monitoring and be controlled at 1-5nm.Not with wafer under the situation that vacuum chamber takes out, subsequently as described in the previous embodiment with additional C 60Tectum is placed on the metal cladding.C 60Thickness be about 5-10nm.Final catalyst mode is C 60/ [Fe, Co, Ni or Cu]/solid carbon/Si.
Embodiment 6
Catalyst precursor from the sandwich structure of silicon wafer load is made carbon nanotube
The catalyzer of Si wafer load is placed in 10 minutes the 1-inch quartz reactor of argon purge.Subsequently, reactor is sealed at both ends and make temperature be raised to 800 ℃ fast, sample was reacted 10 minutes under argon gas.After the cool to room temperature, use the Raman check sample, and sample demonstrates the characteristic that diameter is the Single Walled Carbon Nanotube of 1.4 ± 0.2nm.

Claims (45)

1. one kind produces from carbon source and to have the method that Single Walled Carbon Nanotube that narrow diameter distributes is trooped, and described method comprises:
(a) preparation facilities, described device comprises
Metal level,
With the soccerballene of one deck at least of described metal level one side contacts and
The solid-state carbon source that contacts with described metal level opposite side;
(b) described device is heated to be lower than and makes the distillation of described soccerballene but make described soccerballene and described carbon source be dissolved into temperature in the described metal level; With
(c) growing single-wall carbon nano tube is trooped, and wherein the diameter of at least 80% Single Walled Carbon Nanotube is being present within diameter D ± 5% of the Single Walled Carbon Nanotube in described the trooping in described trooping, and described diameter D is in the 0.6-2.2nm scope.
2. the process of claim 1 wherein that described device comprises the multilayer soccerballene that makes described metal level saturated substantially.
3. the process of claim 1 wherein that described diameter D is in the 1.0-1.8nm scope.
4. the process of claim 1 wherein that described diameter D is in the 1.2-1.6nm scope.
5. the process of claim 1 wherein that described carbon source comprises gaseous carbon source after causing growth.
6. the method for claim 5, wherein said carbon source comprises CO, alcohol or hydrocarbon.
7. the process of claim 1 wherein that described metal level comprises the metal that is selected from Fe, Co, Mn, Ni, Cu and Mo.
8. the method for claim 7, wherein said metal level comprises alloy or other mixtures of Fe, Co, Mn, Ni, Cu and Mo.
9. the process of claim 1 wherein that described metal layer thickness is about 1nm-20nm.
10. the process of claim 1 wherein that described metal layer thickness is about 2nm-10nm.
11. the process of claim 1 wherein that described metal layer thickness is about 3nm-5nm.
12. the process of claim 1 wherein that described temperature is about 500 ℃-700 ℃.
13. the process of claim 1 wherein described temperature be lower than as measure by TGA make as described in the temperature of soccerballene distillation.
14. the method for claim 1, it makes described temperature be elevated to the step of the temperature of the sublimation temperature that is higher than described soccerballene after also being included in and causing growth.
15. the method for claim 14, it also comprises makes described temperature be elevated to 700 ℃-1100 ℃ step.
16. the process of claim 1 wherein that described solid-state carbon source comprises carbon fiber.
17. the process of claim 1 wherein that described solid-state carbon source comprises is selected from vitreous carbon, anthraxolite, crosslinked carbon resin and polyparaphenylene crystalline carbon.
18. the process of claim 1 wherein that the vapour pressure of described soccerballene is less than 760mmHg.
19. the process of claim 1 wherein that the vapour pressure of described soccerballene is less than 730mmHg.
20. a composition, it comprises:
Single Walled Carbon Nanotube is trooped, and wherein the diameter of at least 80% Single Walled Carbon Nanotube is being present within diameter D ± 5% of the Single Walled Carbon Nanotube in described the trooping in described trooping, and described diameter D is in the 0.6-2.2nm scope.
21. the composition of claim 20, wherein said diameter D is in the 1.0-1.8nm scope.
22. the composition of claim 20, wherein said diameter D is in the 1.2-1.6nm scope.
23. one kind produces from carbon source and to have the method that Single Walled Carbon Nanotube that narrow diameter distributes is trooped, described method comprises:
(a) preparation facilities, described device comprises
Metal level,
With the soccerballene of one deck at least of described metal level one side contacts and
The solid-state carbon source that contacts with described metal level opposite side;
(b) described device is heated to is lower than the temperature that makes the distillation of described soccerballene;
(c) described soccerballene of one deck at least and described carbon source are dissolved in the described metal level; With
(d) being grown in the Single Walled Carbon Nanotube that has single Raman peaks in the RBM zone troops.
24. the method for claim 23, wherein said device comprise the multilayer soccerballene that makes described metal level saturated substantially.
25. the method for claim 23, wherein after causing growth, described carbon source comprises gaseous carbon source.
26. the method for claim 25, wherein said carbon source comprises CO, alcohol or hydrocarbon.
27. the method for claim 23, wherein said metal level comprises the metal that is selected from Fe, Co, Mn, Ni, Cu and Mo.
28. the method for claim 27, wherein said metal level comprise alloy or other mixtures of Fe, Co, Mn, Ni, Cu and Mo.
29. the method for claim 23, wherein said metal layer thickness is about 1nm-20nm.
30. the method for claim 23, wherein said metal layer thickness is about 2nm-10nm.
31. the method for claim 23, wherein said metal layer thickness is about 3nm-5nm.
32. the method for claim 23, wherein said temperature are about 500 ℃-700 ℃.
33. the method for claim 23, wherein said temperature be lower than as measure by TGA make as described in the temperature of soccerballene distillation.
34. the method for claim 23, it makes described temperature be elevated to the step of the temperature of the sublimation temperature that is higher than described soccerballene after also being included in and causing growth.
35. the method for claim 34, it also comprises makes described temperature be elevated to 700 ℃-1100 ℃ step.
36. the method for claim 23, wherein said solid-state carbon source comprises carbon fiber.
37. comprising, the method for claim 23, wherein said solid carbon be selected from vitreous carbon, anthraxolite, crosslinked carbon resin and polyparaphenylene crystalline carbon.
38. the method for claim 23, the vapour pressure of wherein said soccerballene is less than 760mmHg.
39. the method for claim 23, the vapour pressure of wherein said soccerballene is less than 730mmHg.
40. one kind produces from carbon source and to have the method that Single Walled Carbon Nanotube that narrow diameter distributes is trooped, described method comprises:
(a) device is heated to is lower than the temperature that makes the distillation of described soccerballene; Described device comprise metal level,
With the soccerballene of one deck at least of described metal level one side contacts and
The solid-state carbon source that contacts with described metal level opposite side;
(b) described soccerballene of one deck at least and described carbon source are dissolved in the described metal level; With
(c) growing single-wall carbon nano tube is trooped, and wherein the diameter of at least 80% Single Walled Carbon Nanotube is being present within diameter D ± 5% of the Single Walled Carbon Nanotube in described the trooping in described trooping, and described diameter D is in the 0.6-2.2nm scope.
41. a generation has the reactor system of the Single Walled Carbon Nanotube of narrow diameter distribution, described system comprises:
Metal level,
With the soccerballene of one deck at least of described metal level one side contacts and
The solid-state carbon source that contacts with described metal level opposite side.
42. one kind produces the method that Single Walled Carbon Nanotube is trooped, described method comprises:
(a) preparation facilities, described device comprises
Metal level and
With the soccerballene of one deck at least of described metal level one side contacts,
Described metal level also contacts with non-solid-state carbon source;
(b) described device is heated to is lower than the temperature that makes the distillation of described soccerballene;
(c) described soccerballene of one deck at least and described carbon source are dissolved in the described metal level; With
(d) growing single-wall carbon nano tube is trooped, and wherein the diameter of at least 80% Single Walled Carbon Nanotube is being present within diameter D ± 5% of the Single Walled Carbon Nanotube in described the trooping in described trooping, and described diameter D is in the 0.6-2.2nm scope.
43. the method for claim 42, wherein said non-solid-state carbon source is a gaseous carbon source.
44. the method for claim 42, wherein said gaseous carbon source is selected from hydrocarbon, CO and alcohol.
45. a method that produces Single Walled Carbon Nanotube, described method comprises:
(a) preparation facilities, described device comprises
Metal level and
With the soccerballene of one deck at least of described metal level one side contacts,
Wherein said metal level is saturated with carbon atom;
(b) described device is heated to is lower than the temperature that makes the distillation of described soccerballene;
(c) described soccerballene of one deck at least and described carbon source are dissolved in the described metal level; With
(d) growing single-wall carbon nano tube is trooped, and wherein the diameter of at least 80% Single Walled Carbon Nanotube is being present within diameter D ± 5% of the Single Walled Carbon Nanotube in described the trooping in described trooping, and described diameter D is in the 0.6-2.2nm scope.
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