CN1418260A - High yield vapor phase deposition method for large scale single walled carbon nanotube prepration - Google Patents

High yield vapor phase deposition method for large scale single walled carbon nanotube prepration Download PDF

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CN1418260A
CN1418260A CN01803478A CN01803478A CN1418260A CN 1418260 A CN1418260 A CN 1418260A CN 01803478 A CN01803478 A CN 01803478A CN 01803478 A CN01803478 A CN 01803478A CN 1418260 A CN1418260 A CN 1418260A
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aerogel
combination
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刘杰
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Duke University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/32—Carbides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/881—Molybdenum and iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8906—Iron and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/32—Freeze drying, i.e. lyophilisation
    • 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
    • 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

Abstract

An improved vapor phase deposition method for the preparation of single walled carbon nanotubes on an aerogel supported metal catalyst. The total yield of single walled carbon monotubes often is at least about 100 % as shown by curves based on the weight of the catalyst, for a reaction time of at least about 30 minutes.

Description

The high yield vapour deposition prepares the method for large-scale single-walled carbon nano tube
Technical field
The present invention relates generally to the method that a kind of vapour deposition prepares single wall carbon nano tube (nanotube), the metal catalyst of wherein said method working load on carrier.More particularly, the present invention relates to a kind of improving one's methods, wherein compare with the existing method of using the pulverulence carrier, described carrier contains aerogel, for example Al 2O 3Aerogel or Al 2O 3/ SiO 2Aerogel.The productive rate of the described single wall carbon nano tube that obtains than existing method of improving one's methods is much higher.
AbbreviationASB tri sec-butoxy aluminum AFM atomic force microscope (acac) 2Psi pounds/square inch of SEM SEM of centimetre C degree centigrade of CVD chemical vapour desposition EtOH alcohol of two (pentanedione base) cm g gram kg kilogram kV kilovolt m rice ml milliliter MW molecular weight MWCNT many walls carbon nano tube nm nanometer SWCNT single wall carbon nano tube sccm standard cubic centimeters per minute STP standard temperature and pressure (STP) Tpa is Pascal TGA thermogravimeter TEM transmission electron microscope too
Background of invention
Since finding carbon nanotube from lijima in 1991, it has been one of active research material in the current research.Referring to, lijima, Vol.354, Nature, pp.56-58 (1991).Because remarkable chemistry and physical properties and the potential application in many different field thereof that this material has, therefore this active research is not very astonishing.
For example, be rolled into cylindrical mode according to the quantity and the Graphene of the concentric walls of Graphene (graphene), carbon nanotube can conduct electricity as metal or can semiconduction.Referring to, Dresselhaus etc., Science of Fullerenes and Carbon Nanotubes, Academic Press, San Diego (1996).
And test shows that single carbon nanotube can play quantum wire and even can make the room temperature transistor.Referring to, Tans etc., Vol.386, Nature, pp.474-477 (1997) vis-a-vis quantum wires and Tans etc., Vol.393, Nature, pp.49-52 (1998) vis-a-vis transistors.
In addition, shown that carbon nanotube has excellent mechanical property and chemical stability.Young's modulus by AFM test determination carbon nanotube and the measurement of thermal vibration shown to have value 1.3Tpa and 1.8Tpa respectively, they are all higher than the value of any other known materials.Referring to, Vol.277 such as Wong, Science, pp.1971-1975 (1997) vis-a-vis AFM and Treacy etc., Vol.381, Nature, pp.678-680 (1996) vis-a-visthermal vibrations.
Therefore, because the emission (ballistic) with chemical stability, very good mechanical properties, metalloid transports performance and rich variability because of the Electronic Performance of different spiralities, make carbon nanotube become the ideal candidates material of interconnected and functional device in high strength composite and the molectronics.
Although carbon nanotube has many uniquenesses and technical important performance, lack the method for producing the q.s material and not only limited the research of fundamental property, and limited more practical exploitation.Find that method low-cost, that high productivity prepares SWCNT has solved the greatest problem that this field faces in the past really and opened the chance of various application.
At present, carbon nanotube is by 3 different technologies synthetic: (1) is arc-over between two Graphite Electrodess, and (2) are by CVD and (3) the laser evaporation carbon target of catalytic decomposition hydrocarbon or CO.With regard to CVD, referring to the international publication number WO89/07163 of Synder etc.; The US 4,663,230 of Tennent etc. (authorizing in 1987); M.Terrones etc., Nature 388,52-55 (1997); Z.F.Ren etc., Science 282,1105-1107 (1998); J.Kong, A.Cassell and H.Dai, Chemical Physics Letters 292,4-6 (1998); J.H.Hafner etc., Chemical Physics Letters 296,195-202 (1998); E.Flahaut etc., Chemical Physics Letters 300,236-242 (1999); S.S.Fan etc., Science 283,512-514 (1999); H.J.Dai etc., Chemical Physics Letters 260,471-475 (1996); H.M.Cheng etc., Applied Physics Letters 72,3282-3284 (1998); With A.M.Cassell, J.A.Raymakers, J.Kong and H.J.Dai, Journal of PhysicalChemistry B 103,6484-6492 (1999).
Laser method and arc process all obtain high-quality SWCNT.Yet the problem that these two kinds of technology run into is to be difficult to the productivity of nano-tube material is increased to technical scale from laboratory scale.
On the other hand, with the disclosed basis that is reported as, the CVD method clearly presents the best prospect of scale operation nano-tube material.This method is at the (US4 of Tennent etc. in 1980,663,230 (authorizing in 1987) and M.S.Dresselhaus, G.Dresselhaus, K.Sugihara, I.L.Spain and H.A.Goldberg are editors such as Graphite Fibers andFilaments.M.Cardona, Springer Series in MaterialsScience 5 Springer-Verlag, New York (1988) vol.5) report is to prepare various carbon materials such as carbon fiber and the wall of manying carbon nano tube than laser method and arc process productive rate height and scale the earth in.
Recently in nineteen ninety, reported by CVD (carbon monoxide or methane) preparation SWCNT and reported preparing blended SWCNT with a large amount of MWCNT and prepare by CVD (benzene or ethene).With regard to carbon monoxide CVD, referring to, H.J.Dai etc., Chemical Physics Letters260,471-475 (1996) and P.Nikolaev etc., Chemical Physics Letters313,91 (1999).With regard to methane CVD, referring to, A.M.Cassell, J.A.Raymakers, J.Kong and H.J.Dai, " Large Scale CVD Synthesis ofSingle-Walled Carbon Nanotubes ", Journal ofPhysical ChemistryB103,6484-6492 (1999) and E.Flahaut etc., Chemical PhysicsLetters 300,236-242 (1999).With regard to benzene CVD, referring to, H.M.Cheng etc., Applied Physics Letters 72,3282-3284 (1998).With regard to ethene CVD, referring to J.H.Hafner etc., Chemical Physics Letters 296,195-202 (1998).Therefore, although the report of the report of ethene and benzene relates to SWCNT separately, their defective is that they always mix with a large amount of MWCNT.
In the CVD of these reports method, only methane CVD method is reported production high purity and high-quality SWCNT material.Yet the productive rate of the methane CVD method of report is low, and best result is that overall yield is 40% (amount that is 10-45 minute catalyzer is the basis) with reaction times up to now, and wherein catalyst cupport is to Al 2O 3Powder or Al 2O 3/ SiO 2On the powder and the surface-area of catalyst/support be about 100m 2/ g.Referring to, Cassell etc., the same.
It is therefore, a kind of that to provide the CVD method of high quality SWCNT with unusual high yield (when for example the reaction times is about 30 minutes at least about 100%) will be ideal.
Summary of the invention and purpose
Therefore, the invention provides working load, for example at Al to aerogel 2O 3Aerogel and/or Al 2O 3/ SiO 2The gas phase process of the metal catalyst on the aerogel.Be used for catalyst/support of the present invention and be by solvent-gel synthetic, remove by the drying step that is selected from supercritical drying, lyophilize and combination thereof then that liquid solvent prepares, wherein preferred supercritical drying.Present method is the vapour deposition carbon compound on catalyst/support.This compound should have 28 or lower molecular weight, and if this compound have higher molecular weight, so this compound should with H 2Mix.Vapour deposition provides enough heats in time enough, so that produce SWCNT on aerogel carried catalyzer.Then, if necessary, these SWCNT can remove from the contained catalyzer of aerogel.Typically, based on the weight of catalyzer, these SWCNT can for example about 100% or bigger high yield production.
Therefore, the objective of the invention is in a preferred embodiment, obtain SWCNT with the high yield that can not obtain up to now.This productive rate is far above existing CVD method, and based on the weight of catalyzer, the best productive rate of described existing CVD method is about 40%.
Therefore, it is a kind of with on a large scale that its advantage is that this discovery provides, and technical scale for example prepares the method for SWCNT material at low cost.
Purposes more of the present invention and advantage are narrated, when with specification sheets and laboratory implementation example and accompanying drawing described below in conjunction with the time, other purpose will be obviously.
The accompanying drawing summary
Fig. 1 shows according to (a) preparation of present method preparation and (b) the typical TGA productive rate graphic representation of purifying SWCNT material in air.
Fig. 2 shows for present method to prepare SWCNT material weight increase and graph of a relation in reaction times when using the methane stream of 1158sccm down for 900 ℃.
Fig. 3 a and 3b are respectively by being presented at Al 2O 3On the contained Fe/Mo catalyzer of aerogel by the photo of the microscope photographing of (a) SEM image (b) TEM image of the SWCNT sample of present method preparation.Sample prepares under about 900 ℃, methane stream.Flow velocity is 1158sccm.Reaction times is 30 minutes.
Detailed Description Of The Invention
The present invention uses novel gas phase process that the single wall carbon nano tube is provided, and uses special catalyst/carrier in the described method when deposited carbon-containing compound.In a preferred embodiment, compare with the existing method of using powder carrier, the present invention is in the beat all increase of single wall carbon nano tube yield aspects.
Term " single wall carbon nano tube " meaning is well known in the art.And, with regard to present method, do not plan to get rid of and can produce simultaneously on a small quantity, many walls carbon nano tube for example＜1%.
Suitable carbon compound can be under STP for steam or can be the compound that under reaction conditions, can be transformed into steam.Preferably, this compound is that molecular weight is 28 or lower.Example has CO, CH 4, and the combination.If the molecular weight of this compound is greater than 28, for example benzene (MW=78) or ethene (MW=30), so this compound should with H 2Mix, for example H 2Volume accounts for 50%.
In order to implement high yield is about 100% or higher preferred implementation, should use the carbon compound of enough flow velocitys, and can be for from about 900sccm to about 1300sccm.
Time enough can be about 0.25 hour to about 7 hours.Enough temperature can be about 750 ℃ to about 1000 ℃.Productive rate can be about 200%, and is about 300%, or higher.
Appropriate catalyst is known any metal catalyst in the preparation nanotube field.Preferred metal catalyst can be Fe/Mo, Fe/Pt and combination thereof.Suitable carriers is to mean being used for any aerogel of air as the dispersion agent gel of normal open super-dry preparation in this term this area.The aerogel carrier can be the powdered carrier that is transformed into aerogel by currently known methods.As discussed in more detail below, drying can be supercritical drying or can be lyophilize, but not plan to comprise the drying that causes xerogel.A kind of preferred aerogel carrier can be Al 2O 3Aerogel carrier, Al 2O 3/ SiO 2Aerogel carrier and combination thereof.
As shown in Figure 1, the productive rate of SWCNT material is by add heat determination by the SWCNT material to preparation in TGA under fluidizing air.The overall yield of SWCNT material, be to calculate divided by the weight residue under 700 ℃ by the weight loss between 300 ℃ and 700 ℃, described productive rate is shown on the longitudinal axis with the increase of % weight, temperature is shown on the transverse axis, wherein said SWCNT material burns in air, and the weight residue under 700 ℃ is assumed to the weight of catalyzer and solid support material.
Also studied the purifying of the material of present method preparation.Because the high amorphism of the aerogel carrier for preparing in present method, remove catalyzer and carrier becomes quite easy from the SWCNT material.Can by in rare HF acid, stir, at another diluted acid (HNO for example 3) the middle backflow, perhaps in diluted alkaline such as NaOH solution, reflux carrier is removed.Fig. 1 has shown that material is at 2.6MHNO 3The middle backflow about 4 hours followed filtering TGA result.
As shown in Figure 2, with regard to the time, use the average yield of catalyst/support to be about 200% with regard to about 900 ℃ of about 60 minutes down typical growth.Find growth in the time of about 6.5 hours maximum yield (weight increase) be about 600%.Present method show productive rate significantly better than the front by A.M.Cassell, J.A.Raymakers, J.Kong, H.J.Dai, Journal of PhysicalChemistry B 103,6484-6492 (1999) Kong, Cassell and Dai, ChemicalPhysics Letters 292, the value of 4-6 (1998) report.
As shown in Fig. 3 a and the 3b, the quality of the SWCNT of preparation is with SEM imaging and TEM imaging representation.
More particularly, as described in Fig. 3 a, the SEM pictorial display of the SWCNT material of preparation the fiber that is perfectly clear of wound web dress network.The diameter of fiber is shown as about 20 nanometers of about 10-.Should be mentioned that the SEM image is a harsh long back material, does not carry out purifying before imaging.
And as described in Fig. 3 b, the TEM pictorial display of SWCNT material observed fiber in the SEM image is actually the single wall carbon nano tube of bunchy.From the diameter of the nanotube of high resolving power TEM determining image is the about 2.7nm of about 0.9-.
SEM and TEM image all show the SWCNT material have with laser method (referring to, A.Thess etc., Science 273,483-487 (1996) and T.Guo, P.Nikolaev, A.Thess, D.T.Colbert and R.E.Smalley, Chemical Physics Letters243,49-54 (1995)) and arc process (referring to, M.Wang, X.L.Zhao, M.Ohkohchi and Y.Ando, Fullerene Science ﹠amp; Technology 4,1027-1039 (1996) and C.Journet etc., Nature 388,756-758 (1997)) the middle similar characteristic of high quality single wall carbon nano tube for preparing.
The SEM image only shows nanotube, and does not show the statement of facts of decolorizing carbon skin (overcoat), and the catalyst/support surface is covered by nano-tube material basically fully.Yet in the TEM image, for example increase with regard to weight, promptly productive rate is higher than about 300% sample, observes the decolorizing carbon skin, and this can remove in the SWCNT production process and/or remove after producing SWCNT.
And present method has reflected that the drying means (as discussing in the following laboratory implementation example) of wet gel is the necessary step of the high performance catalyst (as present method used) of preparation on the aerogel carrier.Drying can be passed through supercritical drying, for example passes through CO 2Supercritical drying is perhaps undertaken by the ethanol supercritical drying, perhaps can for example be undertaken by lyophilize by the lyophilize that makes water, and combination.
Yet, do not plan to comprise the drying that causes xerogel.Fricke, Aerogels, Springer-Verlag, Berlin, Heidelberg, New York, Tokyo (1986) and N.Husing, U.Schubert, Angew.Chem.Int.Ed.37,22-45 (1998) have only discussed and at the following vaporised liquid solvent of envrionment conditions (promptly about STP) gel shunk, and this is owing to the capillary forceful action from liquid/gas interface in the hole of gel makes the vesicular structure collapse, and this contraction will reduce the total surface area and the pore volume of drying material significantly, usually this drying material will be referred to as xerogel.
On the other hand, in the supercritical drying process that temperature is carried out under much larger than STP and pressure much larger than STP, the liquid solvent in the wet gel enters supercritical state, for example under carbonic acid gas tectum (blanket).Therefore, in drying process, in the hole, there is not liquid/gas interface basically.Therefore in final dry catalyst/aerogel, kept the initial vesicular structure in the wet gel basically.
Equally, increasing nanotube is grown on the surface of aerogel carried catalyzer, carbon compound, methane or carbon monoxide among the promptly following embodiment, more difficult being distributed on the catalyst/support.And owing to mention in discussing as top Fig. 3 a and 3b, in the more long-living long-time decolorizing carbon deposition of observing on nanotube down, this carbon coating has further reduced the speed that carbon compound is diffused into catalyst/support.This tectum has been explained the reason that why speed of growth reduces in time shown in Fig. 2.
In a word, found that catalyst/support form that a kind of use can be used for vapour deposition process prepares the novel method of single wall carbon nano tube, preferably with than by the existing obtainable big productive rate of method.Be loaded in Al 2O 3Similar catalyzer on the powder is compared, and the coefficient that this productive rate improves is generally at least 2.5, and often is 5.
The laboratory implementation exampleMaterial
The all material that is used for the laboratory implementation example all be from different suppliers enough the research grade material.
Tri sec-butoxy aluminum (below be abbreviated as ASB), Fe 2(SO 4) 3.4H 2O and two (Acetyl Acetone base) dioxo molybdenum (below be abbreviated as MoO 2(acac) 2) available from Sigma/AldrichChemicals.
SILVER REAGENT nitric acid, ammonium hydroxide and ethanol are available from VWR Scientific Products.
High purity methanol, carbonic acid gas and hydrogen are supplied by National Welders Inc. Example IThe catalyst/support preparation
Catalyst/support is to use D.J.Suh and J.T.Park, and the solvent-gel technique of report also uses supercritical drying to prepare subsequently among the Chemistry ofMaterials 9,1903-1905 (1997).More optional samples come dry by lyophilize.
In a routine test, in round-bottomed flask, under reflux conditions, 23g ASB is dissolved in the ethanol of 200ml as liquid solvent.Then, with the dense HNO of 0.1ml 3,, add in this mixture with 1ml water and 50ml alcohol dilution.
Gains were refluxed 2 hours,, then in this mixture, add 1.38g Fe up to forming settled solution 2(SO 4) 3.4H 2O and 0.38g MoO 2(acac) 2The amount of Fe and Mo is through selecting so that Mo: the mol ratio of Fe: Al=0.16: 1: 16.After refluxing more than 2 hour, mixture is cooled to room temperature, then with the dense NH of 5ml 4OH with the dilution of 5ml water, joins in the mixture under vigorous stirring, so that impel the dissolved metal-salt to form the nano level hydroxide particles and attached on the aerogel.Form gel in the several minutes.
Gains left standstill aging about 10 hours, carried out the supercritical drying step afterwards under the following conditions.
At first, the catalyst/support wet gel is sealed in the high pressure vessel, then it is cooled to about 0 ℃ and at about 830psi (about 59.4kg/cm 2) the following liquid CO that uses 2Be depressed into and be full of container.Carry out solvent exchange step, so that by using liquid CO 2Rinsing vessel for some time makes ethanol liquid solvent and the liquid CO in the gel 2Exchange.
Then, container is heated to about 50 ℃-Yue 200 ℃, at CO 2Critical temperature (31 ℃) on, and pressure is maintained at about 1500psi-2500psi (about 106.4kg/cm 2-176.8kg/cm 2), it is at CO 2Emergent pressure (1050psi, 74.8kg/cm 2) on.This system is kept for some time under these conditions, remain unchanged in temperature afterwards and down pressure is slowly reduced.
At last, temperature is reduced to room temperature.Then, each catalyzer on the aerogel carrier (with the metal hydroxides form) was calcined 30 minutes down in 500 ℃, thereby changed into the metal oxide form.Then before being used for SWCNT growth, by at H 2, 900 ℃ down reduction changed it into metallic forms in 30 minutes.The pressure in this stage is about 830psi (about 59.4kg/cm 2).Zhi Bei each catalyst/support is the catalyzer that is loaded with on highly porous, very thin, free-pouring aerogel in this way, and the surface-area of aerogel is about 500m 2The about 600m of/g- 2/ g.
Perhaps, without CO 2, some samples are carried out supercritical drying or following next dry by lyophilize with ethanol.
Ethanol supercritical drying: the high pressure and the elevated temperature vessel that use 100ml.At least the wet gel of 35ml is joined in the container.Before heating, use N 2Wash this system to drive away air.Then total system is sealed and begins and heat.Temperature keeps system 30 minutes under this temperature, afterwards slow release EtOH after arriving 260 ℃.Discharge and observe about 15 minutes of cost.Then, this system is slowly cooled off and taken out aerogel carried catalyzer.The productive rate of such nanotube with use CO 2Exsiccant is similar.
Lyophilize: the ethanol water in the wet gel is replaced by exchange of solvent.Then, with liquid nitrogen that sample is freezing and put in the freeze drier (Freezone Plus 6, Labconco, Kansas City, Missouri, United States of America).Spend several days with sample complete drying and its productive rate and be lower than and use CO 2Exsiccant.The SWCNT growth
SWCNT makes in the simple vapor deposition apparatus of being made up of pipe furnace and air flow controller.In the typical growth test, the catalyst/support sample of about 50mg is put into the aluminium oxide boat of silica tube.The flow velocity that flows down with 100sccm at Ar is heated to temperature of reaction respectively with each sample, then, changes Ar into H 2(about 100sccm flow velocity) continues 30 minutes, changes methane stream (about 1000sccm) afterwards into and continues 30 minutes.Under about 800 ℃, about 850 ℃, about 900 ℃ and about 950 ℃ each temperature to each sample heating.
Required time is carried out in reaction, and sight is afterwards fallen methane stream and is opened Ar stream and temperature is reduced to room temperature.Then each gains is weighed and characterize.
Characterize
Use TEM imaging and SEM imaging that the SWCNT sample is characterized fully.
The TEM imaging is carried out in operation under 100kV on Philip CM-12 microscope.Ultrasonic 10 minutes of 10ml methyl alcohol by will about 1mg material and on clean carbon lattice dry several suspension prepare the sample that the TEM imaging is used.
Carry out the SEM imaging being placed on by the material after will growing on the conduction carbon ribbon with the beam energy of 4kV on the Hitachi S-4700 microscope.
Relatively the productive rate of the SWCNT material of catalyzer is to go up under fluidizing air, 5 ℃/minute rate of heating at thermogravimeter (SDT 2960 types are available from TA Instruments) to measure.As described in Figure 1, the observation productive rate of measuring by TGA is 100.2%.
Example II
Basically repeat the step of example I, just in the SWCNT process of growth, the time of methyl alcohol stream is that about 60 minutes (rather than about 30 minutes) and temperature are about 900 ℃ (rather than about 800 ℃, about 850 ℃, about 900 ℃ and about 950 ℃ differing tempss), and flow velocity is about 1158sccm (rather than about 1000sccm).The productive rate of measuring by TGA is about 200%.
EXAMPLE III (contrast)
Catalyst/support also is by identical Al 2O 3Wet gel is made, and is just dry different, thereby makes xerogel.Show that at flow catalyzer that about 60 minutes following aerogels are loaded with of about 900 ℃ of methane the productive rate of high purity SWCNT is about 200%, reports as example I.On the other hand, the catalyzer that is loaded with of xerogel shows that under the same conditions weight increases＜5%.
EXAMPLE IV
As be loaded in Al 2O 3Fe/Mo catalyzer on the aerogel repeats its step, just this moment the Fe/Mo catalyst cupport is arrived the SiO for preparing by similarity method 2On the aerogel.
SiO under the same terms (about 900 ℃ of following methane flowed about 60 minutes) 2The weight of the catalyzer on the aerogel increases to about 10%.Therefore, apparent, although SiO 2The aerogel carrier works (promptly about 10%), but the inventive method is preferably used Al 2O 3Aerogel or Al 2O 3/ SiO 2The aerogel carrier is to obtain further excellent raising (being that weight increases to about 100% or bigger).
EXAMPLE V
Basically repeat the step of example I, just use CO replaced C H this moment 4Equally, the temperature of CO stream is about 850 ℃, and the CO flow velocity continues about 200 minutes for about 1200sccm.The result is that productive rate is about 150%.
Example VI
Basically repeat embodiment worker's step, just use Al this moment 2O 3/ SiO 2As the aerogel carrier, replace Al 2O 3Make the aerogel carrier.Obtain substantially the same result, just have more unbodied carbon.
Example VII A (contrast)
It is believed that the more decolorizing carbon that produces in the example VI, this is because as a comparison, Al 2O 3/ SiO 2Aerogel (without any metal catalyst) was tested 30 minutes under 900 ℃ with methane and like this methane has been transformed into decolorizing carbon.
It should be understood that and to change various details of the present invention in the case without departing from the scope of the present invention.And the specification sheets of front only is for purpose of description, is not the purpose in order to limit, and the present invention defines by claims.

Claims (18)

1, a kind of method for preparing the single wall nanotube, comprise: under gas phase condition, carbon compound is deposited on the supported catalyst of the gentle gel carrier of containing metal catalyzer, enough under the reaction conditions of the temperature and time that forms the single wall carbon nano tube on the aerogel carried catalyzer, heating simultaneously.
2, the process of claim 1 wherein that the molecular weight of described carbon compound is 28 or lower.
3, the method for claim 2, wherein said carbon compound is selected from methane, carbon monoxide and combination thereof.
4, the process of claim 1 wherein described carbon compound molecular weight greater than 28 and this compound mix with hydrogen.
5, the method for claim 4, wherein said carbon compound is selected from ethene, benzene and combination thereof.
6, the process of claim 1 wherein that described metal catalyst is selected from Fe/Mo, Fe/Pt and combination thereof.
7, the process of claim 1 wherein that described aerogel carrier is selected from Al 2O 3Aerogel carrier, Al 2O 3/ SiO 2Aerogel carrier and combination thereof.
8, the process of claim 1 wherein described deposition be at enough flow velocitys carbon compound, enough to carry out under the condition of heating to obtain weight with catalyzer under the enough time serve as basic at least about 100% productive rate.
9, the method for claim 8, wherein said enough flow velocitys are the about 1300sccm of about 900sccm-.
10, the process of claim 1 wherein that described aerogel carried catalyzer has about 500m 2The about 600m of/g- 2The surface-area of/g.
11, the process of claim 1 wherein that described aerogel carried catalyzer comes dry by the drying that is selected from supercritical drying, lyophilize and combination thereof.
12, the method for claim 11, wherein said supercritical drying is selected from CO 2Supercritical drying, ethanol supercritical drying and combination thereof.
13, the method for claim 11, wherein said lyophilize are to use the water-cooled freeze-drying dry.
14, the process of claim 1 wherein that described enough heating provide about 750 ℃-Yue 1000 ℃ temperature.
15, the process of claim 1 wherein that the described enough time is at least about 0.25 hour.
16, the process of claim 1 wherein that described productive rate is at least about 100%.
17, the method for claim 1 also comprises single wall carbon nano tube and aerogel carried catalyzer are separated.
18, a kind of method for preparing the single wall carbon nano tube, be included on the supported catalyst that under the gas phase condition carbon compound is deposited to the gentle gel carrier of containing metal catalyzer, wherein carbon compound is selected from methane, carbon monoxide and combination thereof, metal catalyst is selected from Fe/Mo, Fe/Pt and combination thereof, and the aerogel carrier is selected from Al 2O 3Aerogel carrier, Al 2O 3/ SiO 2Aerogel carrier and combination thereof, the drying of aerogel carried catalyzer by being selected from supercritical drying, lyophilize and combination thereof come dry, and described deposition be at enough flow velocitys carbon compound, what enough carry out under the heating under the enough time serves as basic at least about 100% productive rate to obtain with the catalyst weight.
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US20020172767A1 (en) * 2001-04-05 2002-11-21 Leonid Grigorian Chemical vapor deposition growth of single-wall carbon nanotubes
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GB0216654D0 (en) * 2002-07-17 2002-08-28 Univ Cambridge Tech CVD Synthesis of carbon nanoutubes
US6974492B2 (en) 2002-11-26 2005-12-13 Honda Motor Co., Ltd. Method for synthesis of metal nanoparticles
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US7485600B2 (en) * 2004-11-17 2009-02-03 Honda Motor Co., Ltd. Catalyst for synthesis of carbon single-walled nanotubes
US7871591B2 (en) * 2005-01-11 2011-01-18 Honda Motor Co., Ltd. Methods for growing long carbon single-walled nanotubes
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Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4713233A (en) * 1985-03-29 1987-12-15 Allied Corporation Spray-dried inorganic oxides from non-aqueous gels or solutions
US4916108A (en) * 1988-08-25 1990-04-10 Westinghouse Electric Corp. Catalyst preparation using supercritical solvent
JP3285614B2 (en) * 1992-07-30 2002-05-27 日本碍子株式会社 Exhaust gas purification catalyst and method for producing the same
US6004436A (en) * 1996-08-16 1999-12-21 The Regents Of The University Of California Processes for the chemical modification of inorganic aerogels
KR100376197B1 (en) * 1999-06-15 2003-03-15 일진나노텍 주식회사 Low temperature synthesis of carbon nanotubes using metal catalyst layer for decompsing carbon source gas

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