CN101103150A - Method for preparing single walled carbon nanotubes - Google Patents
Method for preparing single walled carbon nanotubes Download PDFInfo
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- CN101103150A CN101103150A CNA2005800466640A CN200580046664A CN101103150A CN 101103150 A CN101103150 A CN 101103150A CN A2005800466640 A CNA2005800466640 A CN A2005800466640A CN 200580046664 A CN200580046664 A CN 200580046664A CN 101103150 A CN101103150 A CN 101103150A
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- walled carbon
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Abstract
Methods of preparing single walled carbon nanotubes are provided. Carbon containing gas is contacted with a supported metal catalyst under reaction conditions to yield at least 90% single walled carbon nanotubes and at least 1 gram single walled carbon nanotubes/gram metal catalyst. The support material may be calcined at temperatures between 150 and 600 DEG C, and may have at least one oxidized planar surface. Reaction conditions include less than 10 atmospheres pressure and less than 800 DEG C.
Description
Cross reference information
The application requires the U.S. Provisional Application the 60/630th of submission on November 24th, 2004, No. 946, the U.S. Provisional Application the 60/630th that on November 24th, 2004 submitted to, the U.S. Provisional Application the 60/628th that No. 781 and on November 16th, 2004 submit to, No. 498 rights and interests and priority, its each comfortable this is incorporated the application by reference fully into.
Background of invention
Technical field
The present invention relates to the preparation method of Single Walled Carbon Nanotube.More specifically, the present invention relates under the reaction condition of commericially feasible, prepare the method for the closs packing array of carbon nanotube bundles or Single Walled Carbon Nanotube.
Description of Related Art
CNT
The invention belongs to CNT (having another name called fibrillation) field.CNT is that diameter is less than 1.0 μ m, preferably less than 0.5 μ m, more preferably less than the vermiform carbon deposits of 0.2 μ m.CNT can be that many walls (promptly having the graphite linings that is roughly parallel to the nanometer tubular axis more than) also can be (promptly the having only a graphite linings that is parallel to the nanometer tubular axis) of single wall.The known CNT that also has other type is as fishbone fibrillation (for example, wherein graphite linings is arranged with herringbone pattern with respect to tubular axis) etc.During generation, the form of CNT can be discontinuous nanotube, nanotube aggregation (the fine and close microcosmic particle structure that promptly comprises snarly CNT) or both mixtures.
CNT is different with commercially available continuous carbon fibre.Such as, the diameter of continuous carbon fibre (always greater than 1.0 μ m and be generally 5-7 μ m) much larger than CNT (generally less than 1.0 μ m).CNT also has intensity and the conductance that is much better than carbon fiber.
CNT also is different from carbon such as the standard graphite and the carbon black of other form on physics and chemical property.Standard graphite is because its structure can proceed to oxidation almost completely saturated.In addition, carbon black is to be the have graphite-structure amorphous carbon of spheric granules form of (surrounding unordered nuclear as carbon-coating) usually.On the other hand, CNT has one or more orderly graphitic carbon atomic layers around the substantially concentric arrangement of nanotube cylinders axle.These differences especially make and are difficult to predict the nanotube chemistry with graphite and carbon black.
And people recognize further that many walls also are different with Single Walled Carbon Nanotube each other.For example, multi-walled carbon nano-tubes has a plurality of graphite linings along the nanometer tubular axis, and Single Walled Carbon Nanotube has only a graphite linings on the nanometer tubular axis.
The method of making multi-walled carbon nano-tubes also is different from the method for making Single Walled Carbon Nanotube.Particularly, obtain many walls still is the various combination that Single Walled Carbon Nanotube needs catalyst, catalyst carrier, raw material and reaction condition.Some combination also can obtain the mixture of many walls and Single Walled Carbon Nanotube.
Thereby, determine whether can be used for to viable commercial someway extensive when making desired CNT, often need to examine or check two features.The firstth, selection of catalysts (for example, this catalyst can mainly produce the carbon product that Single Walled Carbon Nanotube still can mainly produce multi-walled carbon nano-tubes or other form).The secondth, the productive rate of catalyst (for example, the carbon products weight of Unit Weight catalyst system therefor generation).
The method that forms multi-walled carbon nano-tubes is well known.The Chemistry and Physics of Carbon of Baker and Harris for example, Walker and Thrower chief editor, Vol.14,1978, the 83 pages; Rodriguez, N., J.Mater.Research, Vol.8, the 3233rd page (1993); Oberlin, A. and Endo, M., J.of Crystal Growth.Vol.32 (1976), 335-349 page or leaf; The U.S. Pat 4,663,230 of Tennent; The U.S. Pat 5,171,560 of Tennent; Iijima, Nature 354,56, and 1991; Weaver, Science 265,1994; De Heer, Walt A., " Nanotubes and the Pursuit of Applications, " MRSBulletin, in April, 2004, or the like.These lists of references are all incorporated into by reference at this.
The method of commercial known formation multi-walled carbon nano-tubes is all very high on selectivity (for example, the amount of multi-walled carbon nano-tubes surpasses 90% in the product) and productive rate (for example every pound of catalyst produces 30 pounds of multi-walled carbon nano-tubes).
The method of making Single Walled Carbon Nanotube also is to know the sixth of the twelve Earthly Branches.For example " Single-shell carbonnanotubes of 1-nm diameter ", S Iijima and T Ichihashi Nature, vol.363, the 603rd page (1993); " Cobalt-catalysed growth of carbon nanotubes withsingle-atomic-layer walls, " D S Bethune, C H Kiang, M S DeVries, GGorman, R Savoy and R Beyers Nature, vol.363, the 605th page (1993); People's such as Bethune U.S. Pat 5,424,054; Guo, T., Nikoleev, P., Thess, A., Colbert, D.T., and Smally, 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); People's such as Smalley U.S. Pat 6,761,870 (WO 00/26138); " Controlled production ofsingle-wall carbon nanotubes by catalytic decomposition of CO onbimetallic Co-Mo catalysts, " Chemical Physics Letters.317 (2000) 497-503; U.S. Pat 6,333,016 of people such as Resasco or the like.These lists of references are all incorporated into by reference at this.
Yet different with the multi-wall carbon nano-tube Manifold technology, the method for the formation Single Walled Carbon Nanotube of knowing the sixth of the twelve Earthly Branches does not generally reach industrial acceptable selectivity and yield level under the reaction condition of commericially feasible at present.For example, at people such as Maruyama " Low-temperature synthesis ofhigh-purity single walled carbon nanotubes from alcohol " ChemicalPhysics Letters, 360, the 229-234 page or leaf discloses a kind of method that obtains the high-purity Single Walled Carbon Nanotube under vacuum or utmost point low-pressure (for example 5 holders) in (on July 10th, 2002) (it is incorporated into by reference at this).On plant-scale reactor, keep extremely low like this pressure commercial be infeasible.The U.S. Pat 6,333,016 of other list of references such as Resasco also discloses the high selectivity of Single Walled Carbon Nanotube, but fails to show the productive rate of commericially feasible.
Thereby, need a kind of method of under the reaction condition of commericially feasible, making Single Walled Carbon Nanotube with industrial acceptable activity, selectivity and yield level.
Summary of the invention
The invention provides the method for preparing Single Walled Carbon Nanotube, comprise that making carbonaceous gas and metal supported catalyst is to contact under at least 90% Single Walled Carbon Nanotube and the reaction condition of productive rate at least 1 gram Single Walled Carbon Nanotube/gram metallic catalyst in selectivity.
More specifically, the invention provides a kind of method for preparing Single Walled Carbon Nanotube, its step is included in 150 ℃-600 ℃ temperature calcinated support material, and wherein said carrier material has at least one plane surface; Preparation comprises the supported catalyst of metal catalysts precursors and described burnt carrier material; Randomly calcine and/or the described supported catalyst of prereduction; With make this supported catalyst and carbonaceous gas and give birth under the reaction condition of at least 90% Single Walled Carbon Nanotube and contact being enough to produce the volume production that surpasses 1 gram Single Walled Carbon Nanotube with every gram metallic catalyst; Pressure in the wherein said reaction condition is greater than about 1 but less than about 10 atmospheric pressure, and the temperature in the described reaction condition is for being lower than 800 ℃.Preferably, the described plane surface of carrier material is in oxidation state.This plane surface (that is) that does not have the carrier material of any oxide or oxygen groups for oxidation for having oxide on this surface that makes carrier material, preferably before carrying out method of the present invention with the carrier material oxidation.The oxidizing temperature that is fit to can be and is higher than 1000 ℃.
In a kind of optional embodiment, calcining step can be carried out after the step of preparation supported catalyst.In another embodiment, calcining step both can also can be carried out after it before the step of preparation supported catalyst.
Preferred metallic catalyst comprises Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cr, W, Mo, Mn, Ni or its mixture.Preferred carrier material be platelet, thin slice or planar substrate form and by aluminium oxide (Al
2O
3), magnesia (MgO), silica (SiO
2), Mg (Al) O
x, ZrO
2, molecular sieve zeolites, glass, quartz, clay, hydrotalcite, talcum, aluminium foil or silicon makes.
Preferred range of reaction temperature is 400-800 ℃, more preferably 500-750 ℃, and further preferred 550-650 ℃.Preferred reaction pressure scope is 0.5-10atm, more preferably 1-5atm, further preferred 1-2atm.
Should know that reactant gas must provide with the pressure of a little higher than reaction zone pressure so that they need not just can inflow reactor by pressurization or other power.
Carrier material can randomly stand plasma treatment before being used to prepare supported catalyst.Available plasma comprises based on F
2, O
2, NH
3, He, N
2And H
2, other chemism or inert gasses, one or more active gases and one or more inert gas maybe can carry out those of other combination of the gas of plasma initiated polymerization such as methane, ethane or acetylene.
In the oxygen containing system of those carbon sources, preferred condition also is included in the growth course of Single Walled Carbon Nanotube and keeps favourable oxidizing potential by the dividing potential drop of control oxidizing gas such as molecular oxygen, carbon dioxide or water at reaction zone.When carbon source is hydrocarbon, advantageously when reaction is carried out, the hydrogen in the reacting gas is remained on above stoichiometric level.
The present invention also include help reaction zone or in subsequently Disengagement zone from method, system and the catalyst configuration of catalyst results Single Walled Carbon Nanotube.Recorded and narrated preferred catalyst granules structure.
The present invention also will find out from following explanation to the preferred embodiments of the invention other improvement that prior art provides.This explanation never is to limit the scope of the invention, and only provides the engineering construction example of present embodiment preferred.Scope of the present invention will provide in claims.
The accompanying drawing summary
Fig. 1 is the method schematic diagram for preparing the Single Walled Carbon Nanotube dense array on planar substrate.
Fig. 2 is according to the representative Raman spectrum of embodiment 4-6 at the product of 600 ℃ and 700 ℃ formation.
Fig. 3 is at the scanning electron micrograph (SEM) of the Single Walled Carbon Nanotube dense array of 600 ℃ of preparations according to the present invention.
Fig. 4 is at the transmission electron microscope photo (TEM) of the Single Walled Carbon Nanotube dense array of 600 ℃ of preparations according to the present invention.
Fig. 5 is the Raman spectrum of the product that obtained according to embodiment 9.
Fig. 6 A-C is the Raman spectrum of the product that obtained according to embodiment 10.
Fig. 7 A-E is the Raman spectrum of the product that obtained according to embodiment 11.
DESCRIPTION OF THE PREFERRED
The invention provides a kind of new method of making Single Walled Carbon Nanotube, it can be issued to industrial acceptable selectivity and yield level at the reaction condition of commericially feasible.
In preferred embodiments, a kind of method for preparing Single Walled Carbon Nanotube is provided, has comprised carbonaceous gas and metal supported catalyst are contacted producing under at least 90% Single Walled Carbon Nanotube and the productive rate reaction condition at least 1 gram Single Walled Carbon Nanotube/gram metallic catalyst.Preferred reaction condition comprises and is lower than 800 ℃ and less than 10 atmospheric pressure.
Reaction can be carried out at any popular response device that is used for preparing CNT.
The amorphous carbon that does not generally contain any pyrolytic deposition according to the Single Walled Carbon Nanotube of this preferred embodiment manufacturing.The diameter range of this Single Walled Carbon Nanotube is the 0.5-10 nanometer, preferably less than 5 nanometers, more preferably between the 0.5-1 nanometer.
In addition, Single Walled Carbon Nanotube can be with independent nanotube or nanotube aggregation (densification, the microscopic particles structure that promptly comprise snarly CNT) or the growth of both mixed forms.Because its high nucleation efficient, the method for this preferred embodiment allow Single Walled Carbon Nanotube with dense packing array, bundle or the rope of Single Walled Carbon Nanotube or the form growth of so-called " single-walled nanotube woods ".One " single-walled nanotube woods " can comprise even or uneven minor structure.For example, the single-walled nanotube woods can comprise a plurality of ropes formed of Single Walled Carbon Nanotube by orientation, and the diameter of described rope can be 2-20nm, more preferably less than 10nm.In preferred embodiments, the independent Single Walled Carbon Nanotube of all of manufacturing all has the approximate or basic diameter that equates, and all minor structure ropes also all have the approximate or basic diameter that equates.The density of described array, bundle, rope or woods can be 10
16-10
18Nanotube/m
2Between.In one embodiment, single-wall carbon nanotube array or woods can be arranged parallel to each other or substantially parallel.
In one embodiment, this method causes growing single-wall carbon nanotube array, bundle, rope or woods, and wherein at least 50% of metallic catalyst exposed surface area is covered by the matrix of single wall nanotube.In another embodiment, the method reaches and surpasses 75% nucleation efficient.
Carbonaceous gas
Carbonaceous gas can be that any gaseous carbon source is as having the C of hetero atom H, O, N, S or Cl
1-C
6Compound, randomly mix with hydrogen.Preferred carbon monoxide.Other available carbonaceous gas includes but not limited to unsaturated and saturated aliphatic hydrocarbon such as methane, ethane, propane, butane, hexane, ethene, acetylene, propylene; The organic compound of oxygenate such as acetone; Aromatic hydrocarbon such as toluene, benzene and naphthalene.Also can use alcohol as methyl alcohol, ethanol, propyl alcohol etc.
Carbonaceous gas can be the mixture of aforementioned any gas or may further include other gas such as hydrogen, nitrogen or inert gas.A kind of preferred carbonaceous gas is the mixture of carbon monoxide and hydrogen.Carbonaceous gas can further comprise oxygen-containing component.Preferred oxygen-containing component comprises CO
2, H
2O or O
2
Carbonaceous gas can adopt in any conventional method input reactor.In addition, carbonaceous gas can be at reaction form supply response device with Continuous Flow when carrying out continuously, thereby also can with regard to being stored in reaction be carried out in mode in batches before reaction.Carbonaceous gas is before the supply response device or can further be preheating to the temperature of requirement before reacting.
Metal supported catalyst
The catalytically-active metals that is used to make Single Walled Carbon Nanotube comprises the metal from group VIII (for example Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt) or VIb family (for example Cr, W, Mo).Preferred metals is drawn together Fe, Co, Mn, Ni, W and Mo.Also can use analog or the derivative such as the metal carbonyl (for example molybdenum carbonyl, carbonyl iron or the like) of catalytically-active metals.Also can use the mixture of any catalytically-active metals, comprise bimetallic or three metallic combinations.
For forming metal supported catalyst, can use any known method usually that metallic catalyst is deposited on the carrier.These methods be usually included under the situation that carrier material exists mix, evaporation and/or calcining metallic catalyst or metal catalysts precursors.Other method comprises equivalent impregnation, dipping, precipitation, co-precipitation or chemistry or physical absorption.Perhaps, carrier material is contacted with the solution of containing metal catalyst or metal catalysts precursors or immerse wherein, dry then and/or calcining.
Preferred use is not dissolved in the aqueous solution of the carboxylate of the Fe of water or Co salt, particularly Fe and Co substantially.The aqueous solution of the acetate of preferred especially Fe and Co.Mo is a kind of preferred co-catalyst, also preferably deposits from the carboxylic acid salt solution of Mo.
Carrier can be by aluminium oxide (Al
2O
3) or magnesia (MgO) make.Other available carrier material comprises silica (SiO
2), Mg (Al) O
x, ZrO
2, molecular sieve zeolites, glass, quartz, clay, hydrotalcite, talcum, aluminium foil, silicon and other known catalyst carrier.Preferably the surface of carrier contains aerobic or oxide groups.Therefore, preferred carrier material is a silica.Can or adopt known method to handle with the carrier material oxidation with deposition oxy radical or oxide on the surface of carrier material or plane surface.For example, can be higher than 1000 ℃ temperature with silicaization to form or to produce silica surface.
Carrier can be the aggregate form of tabular, prism-shaped or strip crystal.Perhaps, carrier material can be made of (for example Degussa be fuming aluminium oxide) spherical particle that can not split plane surface or aggregation.In preferred embodiments, carrier is small pieces, sheet form, or makes that carrier surface itself is (being planar substrate) of flat form.
In the most preferred embodiment, carrier material has the plane surface of at least one oxidation.
The carrier material of other type comprises carbon nano tube structure such as CNT aggregation, three-dimensional network or rigid porous structure.The CNT aggregation can comprise people's such as Tennent U.S. Pat 5,165,909 by any traditional methods preparation; People's such as Moy U.S. Pat 5,456,897; The U.S. Pat 5 that people such as Snyder submitted on May 1st, 1991,707, PCT application US 89/00322 (" the CarbonFibrils ") WO89/07163 that submitted on January 28th, 916 and 1989, the U.S. Pat 5 that people such as Moy submitted on August 2nd, 1994,456,897 and the PCT application US 90/05498 that submits to September 27 nineteen ninety, (" Battery ") WO 91/05089, the U.S. Pat 5 that people such as Mandeville submit on June nineteen ninety-five 7,500, the U.S. Pat 5 that on August 2nd, 200 and 1994 submitted to, 456,897 and the U.S. Pat 5,569 submitted on October 11st, 1994 of people such as Moy, disclosed those methods in 635, above-mentioned all documents are all incorporated into by reference at this.Can use any traditional methods to make rigid porous structure, comprise people such as Tennent in U.S. Pat 6,432, in 866 disclosed those, this document is incorporated into by reference at this.Three-dimensional network also can use any traditional methods to obtain, and comprises people such as Tennent in U.S. Pat 5,968, in 650 disclosed those, this document is incorporated into by reference at this.
In addition, before deposition or metal-loaded catalyst, the surface of the carrier material of oxidation may need to carry out preliminary treatment to remove surperficial adsorbed organic matter and/or moisture.One of pretreated method is to handle with alcoholic solvent such as ethanol or propyl alcohol.A kind of preferred preprocess method is with gas such as oxygen carrier material to be carried out plasma treatment.Other available plasma comprises that those are based on F
2, O
2, NH
3, He, N
2And H
2, the plasma of other chemism or inert gas or their mixture.This plasma treatment has the oxidation that helps the surface.
Also can adopt method such as the chemical treatment or the additional calcination in air of the oxygen groups density of other known raising surfaces of carrier materials.
Reaction condition
An importance is the Single Walled Carbon Nanotube productive rate that can obtain commericially feasible at the reaction condition (for example pressure, temperature) of commericially feasible down in the method for preferred embodiment.
Aspect pressure, it is found that the method for preferred embodiment can equal, approximate or near carrying out under the atmospheric pressure.This pressure condition will be eliminated vacuum or be used for manually needs to the compression pump of reative cell decompression or pressurization.Vacuumizing is disadvantageous especially: not only have atmospheric air to bleed to cause the danger of exploding, the low-density of subenvironment gas has also limited the productivity ratio of per unit volume.Perhaps, catalytic reaction also can be less than 10 atmospheric pressure, between 0.5-10 the atmospheric pressure, preferably between 1-5 atmospheric pressure, or more preferably carry out between 1-2 atmospheric pressure.
In addition, aspect temperature, it is found that the method for preferred embodiment can be carried out under than the relatively low temperature of the representative temperature that forms CNT by cartalytic decomposition effect.Preferably, be reflected at and be lower than 800 ℃, more preferably between 500-750 ℃, still more preferably under the temperature between 550-650 ℃, carry out.Other possible temperature range comprises 500-700 ℃ or 550-700 ℃.
The continuous method of preferred employing.Should be appreciated that a kind of method can be continuous but be still in batches aspect catalyst and the solid product simultaneously aspect gas.Can regulate the gas phase composition and send remaining gas back to reaction zone by the separating step outside reaction zone in method continuous on the gas phase.Gas can cool off before telling pure gas-phase reaction product and before recompression.Obviously, if the charging of compressor through supercooling compression energy will be minimized.Recycle gas can be reheated before returning reaction zone.The pure gas that will consume in reactor is supplied with and can be added also input reactor independently of this recycle gas.
Oxidizing potential by the control reaction zone can produce Single Walled Carbon Nanotube effectively.The method of preferred control oxidizing potential when carbon source is carbon monoxide, is the amount of carbon dioxide in the control reaction zone.Because CO
2Be the product of desired following reaction,
2CO→C(SWT)+CO
2
This can be by the conditioned reaction district charging rate, dash and sweep speed and recirculation rate is realized, all these is within the technology of this area.It is believed that CO
2Can cause making the amorphous carbon of catalyst poisoning by following reaction equation with the meeting of not expecting
C (undesirable)+CO
2→ 2CO
Reaction, thus CO is returned in the reactant mixture.
Other oxygen source that can be used for reducing the amount of undesirable carbon comprises molecular oxygen, N
2O and water.
C (undesirable)+O
2→ CO
2
C (undesirable)+N
2O → N
2+ CO
C (undesirable)+H
2O → H
2+ CO
But, in system, make water also can generate hydrogen by water gas shift reaction based on carbon monoxide:
H
2O+CO→H
2+CO
2
In the reaction based on hydrocarbon, the undesirable carbon that forms on the catalyst can be removed by the stoichiometry that keeps the hydrogen dividing potential drop to surpass in the following reaction of being carried out:
Hydrocarbon → C (SWT)+H
2
These reactions are carried out under antivacuum, aforesaid practical operation pressure ideally.Good hydrogenation catalyst for example contain Pd, Pt etc. those can promote this effect.In addition, hydrogen is excessive, i.e. the migration of the hydrogen that is absorbed mind-set carrier from metal catalytic may promote the reaction with undesirable carbon.Excessive relevant with the carrier both with catalyst metals.
It must be understood that, on gas phase in the continuous method, can need not " interpolation " described component and a kind of product of gas phase is remained on any desired level at reaction zone.For example, if CO is a carbon source, then can at reaction zone carbon dioxide be remained on any level by the separating step in suitable adjusting downstream.Even the oxidant of expectation is not a product, that part of interpolation oxidant that also only loses in recycling need be added in the recirculation or directly continuously and be added in the reactor.
The present invention also comprises from comprising the imporosity carrier and the method and system of the catalyst results single-walled pipe of the base material of the single-walled pipe of having grown on it.Usually, supported catalyst comprises all base materials, and thickness is less than about 0.5mm, preferably less than about 0.1mm.After single-walled nanotube has been grown on this catalyst, can be by product being broken into less aggregation and as described below to the described pipe of its further processing results.
Results can be undertaken by several modes.In one approach, single-walled pipe is separated from catalyst carrier within reaction zone.In another approach, they separate from catalyst carrier after reactions steps is finished.In two kinds of methods, Gu this solid-separation all can adopt differential fluidisation to carry out.In any method, can advantageously will separate the catalyst recycle of single-walled pipe to reaction zone.
For handle supported catalyst effectively and in reaction zone or in Disengagement zone subsequently separating single-wall pipe from it, advantageously catalyst carrier is cylindrical, sphere or cubic configuration.Desirably, cylindrical or spherical supported catalyst has 0.25 micron minimum diameter and the maximum gauge that approximates the single-walled pipe length of being grown.The maximum gauge of preferred carrier is about 100 microns.
The particle diameter lower limit of supported catalyst, is based on the imporosity catalyst granules and has enough external surface areas and serve as the discovery that commercial available base material need not independent results step for Single Walled Carbon Nanotube growth by 0.25 micron.The particle diameter upper limit of supported catalyst is based on the order of magnitude that adopts independent results step and this diameter height for the SWT that grown on the outer surface of this catalyst granules, it will limit productive rate much smaller than 100% although consider the density reason.
Preferably grow the Single Walled Carbon Nanotube of length-specific and aggregate size to simplify the results Single Walled Carbon Nanotube and to its step of further handling.In general, the size easier processing of aggregation uniformly substantially.In addition, can avoid generating carbon nanotube bundles long, loose accumulation by the length of limiter tube.Therefore, preferably prepare length less than 1cm, preferably less than 5mm, aggregation diameter Single Walled Carbon Nanotube aggregation substantially uniformly.
In a method embodiment, supported catalyst will rest on reaction zone, and the Single Walled Carbon Nanotube aggregation will be denuded this catalyst granules and removed from reaction zone in product gas flow.This aggregation is removed and can strengthen by comprise mechanical organ in reaction zone by what abrasion realized from catalyst granules.
When comprising an independent results district in this method, the gas that breaks away from reaction zone can not be cooled before entering reaction zone yet.In both cases, leave catalyst and the gas of gathering in the crops the district and all can be recycled to reaction zone.Can at first sieve and before it is recycled, remove to dash and sweep stream catalyst.Equally, gas stream also can therefrom be removed earlier before recirculation towards sweeping stream or handling to remove product such as CO
2Or H
2
These instructions of the application have been arranged, according to the result of raw material and expectation change or regulate other reaction condition such as reaction time, reactor size or the like is all within those skilled in the art's limit of power.Can estimate that experiment by fair amount just can make the productive rate maximization when adopting certain specific carbonaceous gas or supported catalyst, these also all should fall into the scope of this preferred embodiment.
Raman spectrum
Raman spectrum is the technology that a kind of those skilled in the art of making can characterize the material of being studied.Usually, when producing Raman spectrum, the light of specific wavelength such as laser beam are irradiated onto on the surface of target.Although most of light is reflected away steadily, generally still have the interaction of molecules in sub-fraction and the target and be scattered and produce Ramam effect, it is collected the generation Raman spectrum.Different materials has its own unique spectrum relevant with its existence, so Raman spectrum is a kind of analysis tool useful when differentiating material.
Thereby, use Raman spectrum usually, there is some peak according to some zone at spectrum, differentiate the form of the carbon that exists in the carbonaceous products.For example, in all types of graphite samples such as height-oriented pyrolytic graphite (HOPG), pyrolytic graphite, charcoal and single wall and multi-walled carbon nano-tubes, all exist and be positioned at～1580cm
-1The zone that is called as " G band " at place.For sample, can observe slight migration (～15cm to higher wave number with very small crystal size
-1).When material when containing defectiveness on the graphite plane or at the edge of graphite crystal, can produce the zone (～1355cm that is called as " D band "
-1Yet the position of known this band is depended on laser excitation wavelength strongly).In Single Walled Carbon Nanotube, observed be called as " radially ventilating mode " or " RBM ", generally be lower than 300cm
-1The zone, wherein all carbon atoms all experience equal radial migration.Referring to Dresselhaus, people's such as M.S. " Single Nanotube Raman Spectroscopy, " Accounts of Chemical Research I, 35 volumes, the 12nd phase, 1070-1078 page or leaf (2002), it is incorporated into by reference at this.
In preferred embodiments, this method ratio of obtaining the band of G in its Raman spectrum and the peak area of D band is higher than 2 and have the product of RBM at least.
Electron microscope technique
Another kind of useful means is to pass through electron microscope technique when the carbon product of analyzing by the method preparation of preferred embodiment.In electron microscope technique, electron beam is irradiated onto on the sample, based on the interaction generation image of electronics and sample.Usually particularly use two electron-like microscopes to observe and characterize CNT: transmission electron microscope (" TEM ") and scanning electronic microscope (" SEM ").Embodiment according to the Single Walled Carbon Nanotube of preferred embodiment preparation is provided in Fig. 3 and 4.
Embodiment
Following examples are used to provide to further understanding of the present invention, are used to limit effective range of the present invention absolutely not.
The preparation of embodiment 1-supported catalyst
Silicon wafer is cut to 1cm * 2cm, puts into baking oven and calcined 3-4 hour at air, be cooled to room temperature then in 1100 ℃.After the reason, it is black-and-blue that wafer is herein.In the ultrasonic bath that contains the 2-propyl alcohol, cleaned this wafer 5 minutes then, then air drying.The wafer that this drying of processing is crossed in miniature oxygen plasma reactor is 5 minutes then.On this wafer, deposit the ethanolic solution of forming by 0.01wt% Co and 0.01wt% Mo by dip-coating.Drying is somebody's turn to do the wafer of coating and was calcined 1 hour in air in 450 ℃ then.
The preparation of embodiment 2-supported catalyst
With 10 gram surface areas is 400m
2Silica gel material (the SiO of/g
2) calcined 3 hours in air in 400 ℃, and make it in round-bottomed flask, be cooled to room temperature.To contain Co acetate and Mo acetate and every kind of tenor by the equivalent impregnation method respectively introduces in this silica for the ethanolic solution of 2.5wt%.With this catalyst in 120 ℃ of air dryings, then in 400 ℃ of calcination 2 hours in air.
The preparation of embodiment 3-supported catalyst
With 10 gram surface areas is 400m
2The silica gel material of/g was calcined 3 hours in air in 400 ℃, and made it be cooled to room temperature in glove box, put into round-bottomed flask then.In flask, add Fe content and be the ferrous ethanol solution of the ethyoxyl of 5wt% and make it and silica supports reacted 5 hours under the stirring that continues.Filter slurry then, in 120 ℃ of dryings, and in 400 ℃ of calcination 2 hours in air.Ethanol solution by in flask, adding the Mo ethylate contain 5wt%Mo and make it and carrier reaction under continuing to stir came on sample further loading Mo in 5 hours then.Filter slurry then, in 120 ℃ of dryings, and in 400 ℃ of calcination 2 hours in air.
The preparation of embodiment 4-Single Walled Carbon Nanotube
The catalyst of making among the embodiment 1 is put into 1 inch quartz reactor, use argon purge 30 minutes.When being elevated to 600 ℃ with the speed of 20 ℃/min, temperature of reactor uses 2%H
2/ Ar replaces this purge gas.In case temperature arrives 600 ℃, with the alternative H of CO stream of 400ml/min
2/ Ar mixture, and reaction was carried out 30 minutes.Be 2%H
2After being cooled to room temperature among the/Ar, the preliminary test of wafer is shown to have a black coating.
The preparation of embodiment 5-Single Walled Carbon Nanotube
The catalyst of making among the embodiment 2 is repeated the step described in the embodiment 4.
The preparation of embodiment 6-Single Walled Carbon Nanotube
The catalyst of making among the embodiment 3 is repeated the step described in the embodiment 4.
Embodiment 7-Raman spectrum
The Raman spectrum of the product that record embodiment 4 obtains, its representative pattern as shown in Figure 2, it has shown typical single-walled nanotube feature.
Embodiment 8-electron microscope
Subsequently, in conjunction with SEM and HRTEM (high resolution transmission electron microscope) test sample 4 to determine the form of product.Two analyses show that all product is made up of the Single Walled Carbon Nanotube of high-purity and density.These single-walled pipe are each other basic and aim at or the parallel bundle or the form of rope.The length of these bundles is in the scope of 1-2 μ m, and diameter is in the scope of 0.6-1.5nm.
Embodiment 9-supported catalyst and ethanol
Preparation Fe load capacity is the supported catalyst of about 15wt%, and puts into the reactor center that is in room temperature.Make 3% hydrogen in argon gas pass through reactor when being within 30 minutes that temperature of reactor is promoted to 900 ℃.Temperature of reactor is reduced to 700 ℃ to promote the pipe growth.In 0 ℃ ethanol steam input pipe.Its Raman spectrum does not show that the peak at RBM place and D are with big peak as shown in Figure 5.
Embodiment 10-supported catalyst and ethanol
At 1100 ℃ with the air oxidation silicon wafer.Wafer ultrasonic wave in propyl alcohol is cleaned, clean, and in ratio is 0.01% solution of 1: 1 Co acetate and Mo acetate, carry out dip-coating with 2cm/ minute hoisting velocity with plasma.In 450 ℃ supported catalyst was calcined 1 hour then.
Carry out three groups of test A, B and C.
In test A, in the reactor of pressure, provide the ethanol steam for 7 millimetress of mercury.Make 2% H by speed with 1000ml/min
2/ Ar by containing the ethanol that is maintained at 0 ℃ the hold-up device and only make 70% air communication cross gas diverter to enter reactor and control reactant concentration.Being reflected at 800 ℃ carried out 20 minutes.Raman spectrum as shown in Figure 6A, has shown the medium peak that is positioned at RMB and has been positioned at the small peak that D is with.SEM has shown the thick Single Walled Carbon Nanotube pad that is about the 200-500 nanometer thickness.
In test B, in the reactor of pressure, provide the ethanol steam for 3 millimetress of mercury.Make 2%H by speed with 1000ml/min
2/ Ar by containing the ethanol that is maintained at 0 ℃ the hold-up device and only make 30% air communication cross gas diverter to enter reactor and control reactant concentration.React at 700 ℃.Raman spectrum, shown in Fig. 6 B and SEM observation confirmed good single-walled nanotube selectivity and had only seldom or do not had the strong signal of the cleaning products of amorphous carbon.
In test C, in the reactor of pressure, provide the ethanol steam for 1 millimetres of mercury.Make 2%H by speed with 1000ml/min
2/ Ar by containing the ethanol that is maintained at 0 ℃ the hold-up device and only make 10% air communication cross gas diverter to enter reactor and control reactant concentration.React at 600 ℃.Raman spectrum shown in Fig. 6 C, has shown the weak signal that is positioned at RBM.
Embodiment 11-supported catalyst and carbon monoxide
At 1100 ℃ with the air oxidation silicon wafer.Wafer ultrasonic wave in propyl alcohol is cleaned, clean, and in ratio is 0.01% solution of 1: 1 Co acetate and Mo acetate, carry out dip-coating with 2cm/ minute hoisting velocity with plasma.In 450 ℃ supported catalyst was calcined 1 hour then.
Carry out two groups of tests, A and B.
The test A in, at first in 700 ℃ reactor with 2%H
2/ Ar gas reduces supported catalyst.Speed with 400ml/min provided CO gas 30 minutes to reactor.Raman spectrum shown in Fig. 7 A, has shown good peak that is positioned at RMB and G band and the small peak that is positioned at the D band.
The test B in, at first in 600 ℃ reactor with 2%H
2/ Ar gas reduces supported catalyst.Speed with 400ml/min provided CO gas 30 minutes to reactor.Raman spectrum shown in Fig. 7 B, has shown good peak that is positioned at RMB and G band and the small peak that is positioned at the D band.
The Raman spectrum of test A and B is combined among Fig. 7 E, illustrates that carbon product has bigger growth at 600 ℃ of ratios at 700 ℃.
The wafer and the carbonaceous gas of embodiment 12-load
A slice silicon wafer is heated to several hrs more than 1000 ℃, is cooled to room temperature then.The surface of silicon wafer will become blueness.Also can adopt other planar substrate.
Immerse wafer in alcoholic solution such as the propyl alcohol and carry out ultrasonic wave and clean.Then wafer is carried out plasma treatment.
Wafer is immersed in the solution of containing metal catalyst then.For example, the acetate solution of 0.01wt% Co and 0.01wt% Mo.In baking oven, under air atmosphere, calcine wafer then with temperature above 400 ℃.
Wafer catalyst after will calcining is afterwards put into reactor and is contacted with a kind of reducing gas mixture when temperature is elevated to preferred temperature scope (for example 550-650 ℃).
When arriving preferred temperature, replace this reducing gas mixture with carbonaceous gas such as CO.Can carry out preheating to described carbonaceous gas.Cooling reactor.Can in reactor, feed identical reducing gas mixture once more.
It is black that the gained wafer is estimated.Raman spectrum estimates to show strong RBM and G band.SEM estimates to show the Single Walled Carbon Nanotube growth of cleaning.
Used term and wording all only are illustrative rather than definitive thereof, and do not get rid of their any coordinate when using these terms or measure, are appreciated that within the scope of the invention and can make various improvement.
Claims (34)
1. method for preparing Single Walled Carbon Nanotube, its step comprises:
Preparation comprises the supported catalyst that loads on the metallic catalyst on the carrier material, described carrier material have at least one plane surface and
Described supported catalyst is contacted under being enough to the reaction condition of every gram metallic catalyst generation above the Single Walled Carbon Nanotube of the volume production living 90% of 1 gram Single Walled Carbon Nanotube with carbonaceous gas at least,
Pressure in the wherein said reaction condition is greater than about 1 but less than 10 atmospheric pressure, and the temperature in the described reaction condition is for being lower than 800 ℃.
2. method for preparing Single Walled Carbon Nanotube, its step comprises:
Preparation comprises the supported catalyst that loads on the metallic catalyst on the carrier material, described carrier material have at least one oxidation plane surface and
Described supported catalyst is contacted under being enough to the reaction condition of every gram metallic catalyst generation above the Single Walled Carbon Nanotube of the volume production living 90% of 1 gram Single Walled Carbon Nanotube with carbonaceous gas at least,
Pressure in the wherein said reaction condition is greater than about 1 but less than 10 atmospheric pressure, and the temperature in the described reaction condition is for being lower than 800 ℃.
3. method for preparing Single Walled Carbon Nanotube, its step comprises:
At 150 ℃-600 ℃ temperature calcinated support material, described carrier material has at least one plane surface,
The preparation comprise metallic catalyst and described burnt carrier material supported catalyst and
Described supported catalyst is contacted under being enough to the reaction condition of every gram metallic catalyst generation above the Single Walled Carbon Nanotube of the volume production living 90% of 1 gram Single Walled Carbon Nanotube with carbonaceous gas at least,
The pressure of wherein said reaction condition is greater than about 1 but less than 10 atmospheric pressure, and the temperature of described reaction condition is for being lower than 800 ℃.
4. the process of claim 1 wherein that described metallic catalyst is selected from Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cr, W, Mo, Mn, Ni and composition thereof.
5. the method for claim 4, wherein said metallic catalyst is Fe or the Co by the solution deposition of undissolved substantially Fe or Co salt.
6. the method for claim 5, wherein said salt is carboxylate.
7. the method for claim 4, wherein Mo is a co-catalyst.
8. the method for claim 7, wherein said Mo is by the solution deposition of Mo carboxylate.
9. claim 6 or 8 method, wherein said carboxylate is an acetate.
10. the process of claim 1 wherein that described carrier material is platelet, small pieces or planar substrate form.
11. the process of claim 1 wherein that described carrier material is selected from aluminium oxide (Al
2O
3), magnesia (MgO), silica (SiO
2), Mg (Al) O
x, ZrO
2, molecular sieve zeolites, glass, quartz, clay, hydrotalcite, talcum, aluminium foil and silicon.
12. the process of claim 1 wherein that the described temperature in the described reaction condition is 550-600 ℃.
13. the process of claim 1 wherein that the described pressure in the described reaction condition is 1-5 atmospheric pressure.
14. the method for claim 1 further is included in the described supported catalyst of preparation before with the described carrier material of plasma treatment.
15. the method for claim 14, wherein said plasma-based is in F
2, O
2, NH
3, He, N
2And H
2, other chemism or inert gasses, one or more active gases and one or more inert gas maybe can carry out other combination of gas such as methane, ethane or the acetylene of plasma initiated polymerization.
16. the process of claim 1 wherein that described Single Walled Carbon Nanotube makes with the form of Single Walled Carbon Nanotube woods.
17. the process of claim 1 wherein that described Single Walled Carbon Nanotube is 10 with density
16-10
18Nanotube/m
2The form of Single Walled Carbon Nanotube woods make.
18. the method for claim 1 further is included in the step of calcining described supported catalyst before contacting with described carbonaceous gas.
19. a method for preparing Single Walled Carbon Nanotube, its step comprises:
Preparation comprises the supported catalyst of metallic catalyst and carrier material, and described carrier material has at least one plane surface,
150 ℃-600 ℃ temperature calcine described supported catalyst and
Described supported catalyst is contacted under being enough to the reaction condition of every gram metallic catalyst generation above the Single Walled Carbon Nanotube of the volume production living 90% of 1 gram Single Walled Carbon Nanotube with carbonaceous gas at least,
Pressure in the wherein said reaction condition is less than 10 atmospheric pressure, and the temperature in the described reaction condition is for being lower than 800 ℃.
20. a method for preparing Single Walled Carbon Nanotube, its step comprises:
Preparation comprises the imporosity supported catalyst of metallic catalyst and imporosity carrier material,
150 ℃-600 ℃ temperature calcine described supported catalyst and
Described supported catalyst is contacted under being enough to the reaction condition of every gram metallic catalyst generation above the Single Walled Carbon Nanotube of the volume production living 90% of 1 gram Single Walled Carbon Nanotube with oxygen-containing component with carbonaceous gas at least; Pressure in the wherein said reaction condition is greater than about 1 but less than 10 atmospheric pressure, and temperature for be lower than 800 ℃ and
Within the reaction zone or in the reaction zone of a separation from the described catalyst the separating single-wall CNT.
21. the method for claim 20, the particle of wherein said imporosity catalyst are cylindrical, cube shaped or spherical.
22. the method for claim 21, wherein said cylindrical, cube shaped or spherical catalyst granules have 0.25 micron minimum effective diameter and approximate the maximum effective diameter of the Single Walled Carbon Nanotube length of growth in the method.
23. the method for claim 22, wherein said maximum effective diameter are 100 microns.
24. the method for claim 20, the wherein said Single Walled Carbon Nanotube fretting corrosion by wherein in reaction zone separates from catalyst granules, and removes in discharging air-flow.
25. the method for claim 20, wherein said Single Walled Carbon Nanotube is separated from catalyst granules in the Disengagement zone.
26. the method for claim 25, wherein catalyst and/or the discharge gas from described Disengagement zone is recycled to reaction zone.
27. the method for claim 20, wherein said Single Walled Carbon Nanotube is made less than form 1cm, substantially uniform aggregation with diameter.
28. a method for preparing Single Walled Carbon Nanotube, its step comprises:
Preparation comprises the supported catalyst of metallic catalyst and carrier material, and described carrier material has at least one plane surface,
150 ℃-600 ℃ temperature calcine described supported catalyst and
Described supported catalyst is contacted under being enough to the reaction condition of every gram metallic catalyst generation above the Single Walled Carbon Nanotube of the volume production living 90% of 1 gram Single Walled Carbon Nanotube with oxygen containing carbonaceous gas at least;
Pressure in the wherein said reaction condition is greater than about 1 but less than 10 atmospheric pressure, and temperature is for being lower than 800 ℃, and the dividing potential drop of oxygen-containing component is remained on the level that helps the undesirable carbon of oxide deposition on described catalyst.
29. the method for claim 20, wherein said oxygen-containing component are CO
2, H
2O, N
2O or O
2
30. the method for claim 20, wherein by selective control reaction feed, dash and to sweep the dividing potential drop that keeps oxygen-containing component with recirculation rate.
31. the method for claim 20, wherein charging is CO, and the oxygen-containing component that is added is H
2O.
32. a method for preparing Single Walled Carbon Nanotube, its step comprises:
Preparation comprises the supported catalyst of metallic catalyst and carrier material, and described carrier material has at least one plane surface,
150 ℃-600 ℃ temperature calcine described supported catalyst and
Described supported catalyst is contacted under being enough to the reaction condition of every gram metallic catalyst generation above the Single Walled Carbon Nanotube of the volume production living 90% of 1 gram Single Walled Carbon Nanotube with hydrocarbon at least;
Pressure in the wherein said reaction condition is greater than about 1 but less than 10 atmospheric pressure, and temperature is for being lower than 800 ℃, and the dividing potential drop of hydrogen remained on surpasses stoichiometric level so that reaction takes place.
33. the method for claim 32, wherein said catalyst package contains effective hydrogenation component.
34. the method for claim 32, wherein by selective control reaction feed, dash and to sweep the dividing potential drop that keeps hydrogen with recirculation.
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|---|---|---|---|
| US62849804P | 2004-11-16 | 2004-11-16 | |
| US60/628,498 | 2004-11-16 | ||
| US60/630,781 | 2004-11-24 | ||
| US60/630,946 | 2004-11-24 |
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|---|---|
| CN101103150A true CN101103150A (en) | 2008-01-09 |
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