WO2003037792A1 - Synthese a grande echelle de nanotubes de carbone a paroi unique effectuee avec des catalyseurs du groupe viiib potentialises par des metaux du groupe vib - Google Patents

Synthese a grande echelle de nanotubes de carbone a paroi unique effectuee avec des catalyseurs du groupe viiib potentialises par des metaux du groupe vib Download PDF

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Publication number
WO2003037792A1
WO2003037792A1 PCT/SG2002/000255 SG0200255W WO03037792A1 WO 2003037792 A1 WO2003037792 A1 WO 2003037792A1 SG 0200255 W SG0200255 W SG 0200255W WO 03037792 A1 WO03037792 A1 WO 03037792A1
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catalyst
group
mgo
swnts
carbon nanotubes
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PCT/SG2002/000255
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English (en)
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Songbai Tang
Jianyi Lin
Kuang Lee Tan
Xiaobin Wu
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National University Of Singapore
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    • 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
    • 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

Definitions

  • the present invention relates to the synthesis of single- walled carbon nanotubes (SWNTs), and to catalysts used in their synthesis.
  • SWNTs single- walled carbon nanotubes
  • SWNTs Three techniques have been employed for the synthesis of SWNTs: A) arc discharge between two graphite electrodes [Iijima et al., Nature 363 (1993) 603], B) laser ablation of a graphite target [Guo et al., Chem. Phys. Lett. 243 (1995) 49] and C) catalytic decomposition of carbon-containing materials, such as carbon monoxide or hydrocarbons, over metal catalysts [Kong et al., Chem. Phys. Lett. 292 (1998) 4] .
  • the first two methods can produce high quality SWNTs, the quantities produced from both arc discharge and laser ablation are limited, and the associated production costs are high.
  • the catalytic method may be the best choice for the large-scale production of SWNTs as this method is known to successfully yield multi-walled carbon nanotubes (MWNTs) in large-scale quantities [Tennent et al., U.S. Patent No. 5,578,584] .
  • MWNTs multi-walled carbon nanotubes
  • SWNTs were also prepared by catalytic decomposition of benzene [Cheng et al., Appl. Phys. Lett. 72 (1998) 3282] or ethylene [Hafnet et al., Chem. Phys. Lett. 296 (1998) 195; Flahaut et al., Chem Phys. Lett. 300 (1999) 236] .
  • Single-walled carbon nanotubes or a mixture of single-walled and multi-walled carbon nanotubes with high BET surface areas can be produced in accordance with the present invention.
  • the invention also pertains to catalyst preparation and to the controlled growth of SWNTs by variations in catalyst composition.
  • a method for the synthesis of single-walled carbon nanotubes which comprises contacting a carbon containing material with a catalyst comprising at least two transition metals and a support, wherein at least one transition metal is a group VIIIB element and at least one transition metal is a group VIB element.
  • SWNTs are either prepared in a single step process or in a two-step process.
  • SWNTs are prepared by passing a gaseous mixture of a carbon-containing compound and of a reducing compound, at elevated temperature, over a catalyst comprising a group VIIIB metal, a group VIB metal and a support.
  • suitable supports include MgO, Si0 2 , Si0 2 /Al 2 ⁇ 3 , A1 2 0 3 , and aerogel A1 2 0 3 , of which MgO is preferred.
  • the preferred VIIIB metals are Co, Fe and Ni . Of the VIB metals Cr, Mo and W, Mo is preferred.
  • the two-step process the same catalyst is contacted with the reducing agent without a carbon-containing compound being present, and the reduced catalyst is contacted with the carbon-containing compound in a second, separate step.
  • Figure 1 displays the schematic diagram of a fixed-bed reactor.
  • Identification number 1 represents the entry flow of the carbon containing compound and of the gaseous reducing compound, for example CH 4 and H 2 ;
  • 2 is the reactor tube;
  • 3 is the catalyst;
  • 4 is the furnace and 5 is the exit flow.
  • FIG. 2 displays the Thermal Gravimetric Analysis (TGA) curves of the raw carbon nanotubes in 10% 0 2 /Ar, synthesized on catalysts, (a) Coo. 05 Mgo. 95 O (comparative); (b) Moo. 01 Coo. 05 Mgo. 94 O; (c) Moo. 025 Coo. 05 Mgo. 925 O; (d) Moo.0 5 Coo.05Mgo. 9 O
  • TGA Thermal Gravimetric Analysis
  • FIG. 3 displays the Temperature Programmed Reduction (TPR) spectra of Mo x Co y Mg ⁇ _ x - y 0 catalysts, (a) C0 0 . 05 M0 0 . 95 O (comparative) ; (b) Moo.0 1 Mgo. 99 O (comparative) ; (c) O0. 0 iCO 0 . 05 g 0 . 94 O ; ( d) M ⁇ o . ⁇ 25 C ⁇ o . ⁇ 5 Mgo .9 25 0
  • TPR Temperature Programmed Reduction
  • Figure 4 displays the Transmission Electron Microscopy (TEM) images of roughly purified nanotubes synthesised on Mo x Co y Mg ⁇ _ x -yO catalysts.
  • the images of Figure 4 display the effect that varying the catalyst has on the nanotubes formed.
  • the scale is 100 nm/cm (a) Coo. 05 Mgo. 95 O (comparative); (b) and (c) Moo. 0 1Coo.0 5 Mgo. 94 O; (d) and (e) Moo.025Coo.05Mgo.925O; (f) Moo. 05 Coo. 05 Mgo. 9 O; (g) Moo. 075 Coo.0 5 Mgo.875O; (h) Moo. 035 Coo. 07 Mgo. 895 O
  • Figure 5 displays the low frequency Raman spectra of roughly purified materials synthesized on Mo x Co y Mg ⁇ _ x _ y O catalysts, (a) Coo. 0 5Mgo.95O (comparative) ; (b) Moo.01Coo.05Mgo.94O; (c)
  • Figure 6 displays the Transmission Electron Microscopy (TEM) images of roughly purified materials synthesized on Mo x Fe y Mg ⁇ _ x - y O catalysts.
  • the scale is 100 nm/cm.
  • Figure 7 displays the low frequency Raman spectra of roughly purified materials synthesized on Mo x Fe y Mg ⁇ - x _ y O catalysts.
  • SWNTs are prepared by heating the catalyst, for example in an amount of from about 0.2 to 0.5g, which is preferably in powder form, under a flow of a gaseous mixture comprising one or more carbon containing compounds and, optionally, one or more reducing compounds, such as hydrogen or formaldehyde.
  • the carbon containing compound and the reducing compounds are preferably present in a molar ratio of from 8:1 to 1:4 and total flow rate of the gaseous mixture is preferably about 250 cm 3 /min.
  • Flow can be controlled by the use of flowmeters. Carbon nanotubes start growing as soon as the group VIIIB metal is reduced.
  • the concentration of the reducing gaseous compound in the total feed gas is preferably at least 5%, more preferably at least 10% and most preferably at least 20%. There is no upper limit to the concentration of the reducing gaseous compound as long as carbon-containing compounds still remain in the reactor.
  • the furnace temperature is linearly increased up to between 1198K and 1373K, at a rate between 1 and 40 K per minute. More preferably, the catalyst is heated to about 1273K at rate of about 5K/min. The reactor is held at the final temperature for 2 min. Subsequently, the flow of the gaseous mixture is stopped, and the resulting nanotube/catalyst product is optionally cooled down in a flow or under an atmosphere of an inert, oxygen- free gas, for example H 2 .
  • the carbon source used for catalytic decomposition to form SWNTs can be selected from any organic carbon containing compounds, or certain oxides of carbons, that are in the gas phase under the reaction conditions. Preferably used are aliphatic hydrocarbons, aromatic hydrocarbons, oxygen containing hydrocarbons and mixtures thereof.
  • the carbon source can be either saturated or unsaturated. Examples of appropriate carbon sources include methane, ethane, propane, butane, benzene, butene, cyclohexane, ethylene, acetylene, and carbon monoxide, of which methane is preferred.
  • acid can be used to remove the catalyst particles from the SWNTs formed.
  • the acid reacts with the metallic catalyst, rendering it soluble.
  • the raw nanotubes are preferably immersed and stirred in the acid for 5 to 8 hours.
  • the nanotubes can then be filtered, washed with water and dried in an oven.
  • Inorganic acids are preferred. Suitable examples of acids include HN0 3 , HC1, and H 2 SO 4 . Preferably, a 65% solution is used.
  • nanotubes can be carried out in either a fixed-bed or a fluidised-bed reactor. Both reactor types display similar quality and yield .of SWNTs. A plurality, say two or three or more, of these reactors can be linked in series. A standard reactor is depicted in Figure 1
  • the quantity of carbon nanotubes can be determined by Thermal Gravimetric Analysis (TGA) .
  • TGA Thermal Gravimetric Analysis
  • the raw material (without acid purification) is calcined in a flow of 10% 0 2 /Ar, with a heating rate of 4K/min.
  • the yield of carbon materials is defined as:
  • Wi n itiai and W ie ft are the weight left at 473K and 1073K respectively.
  • W ⁇ ⁇ ft is taken as the weight of the catalyst after carbon materials are burnt out in 0 2 .
  • the yield of carbon nanotubes obviously increases with the increase of molybdenum content.
  • the unrefined SWNTs can also be characterised by TEM, Raman spectrometry and BET surface area analysis.
  • the presence of the group VIB metal promoter remarkably increased the yield and improved the quality of the SWNTs obtained.
  • the generation rate of SWNTs was raised in some instances at least 10 times and the formation of amorphous carbon was suppressed.
  • Other transition elements, alone or in mixtures, may also be added to Co/MgO, Fe/MgO or Ni/MgO catalysts as promoters, in place of or in addition to Mo, to yield SWNTs. Examples include the other two stable group VIB metals, chromium and tungsten.
  • the catalyst is preferably prepared by a wet mechanical mixing followed by combustion synthesis.
  • One or more group VIB metal salts and one or more group VIIIB metal salts are weighed and mixed together with a salt of a catalyst support in the desired molar ratio as in, for example, Mo x Co y Mg ⁇ _ x - y O or Mo x Fe y Mgi_ x _ y O, when Mo is used as the Group VIB metal and Co or Fe are used as the Group VIIIB metal.
  • the molar ratio of group VIIIB metal to group VIB metal is preferably in the range of 5:1 To 2:3, and the ratio of group VIIIB metal to catalyst support is preferably in the range of 1:10 to 1:100
  • suitable Group VIIIB metal salts include
  • Group VIB salts include (NH 4 ) 6 Mo0 24 .4H 2 0) , ammonium chromate, ammonium tungstate, ammonium heptamolybdate, and chromium nitrate.
  • Mg (N0 3 ) 2 .6H 2 0 is preferred as catalyst support salt.
  • a swelling agent for example citric acid or urea, and several drops of distilled water, whose amount depended on the weight of the mixture, can be added. Preferably, 2 to 3 ml of water is added per 10 grams of catalyst.
  • the mixture is ground until it is uniform and it is then heated between 673 and 973K for a period of up to 10 minutes.
  • the combustion synthesis is preferentially carried out at 823K for 5 minutes.
  • the mixture is then cooled to room temperature and the obtained foamy material is ground once more to obtain a fine powder of the desire catalyst.
  • the catalyst can also be prepared without a swelling agent by mechanically mixing a group VIB salt with the salts of the group VIIIB metal and of the support, followed by addition of water. The remaining steps of the process are then carried out as described above.
  • the combination of Co or Ni with MgO supports in catalysts is advantageous for producing carbon nanotubes. Without wishing to be bound by any theory, this may be due to the easy formation of fine Co or Ni nanoparticles .
  • a solid solution is easily formed between CoO and MgO due to the approximate equality of the radii of Co 2+ and Mg 2+ ions, which makes the reduction of CoO difficult, as shown in Figure 3a, as CoO is embedded inside the support.
  • Mo-containing catalysts molybdenum may aggregate at the edges of the cobalt particles, as revealed in Co-Mo/A1 2 0 3 catalyst studies by Niemantsverdriet [ Stud. Surf. Sci . Catal .
  • SWNTs were confirmed by TEM image, as shown in Figure 4. Besides SWNT bundles, many individual tubes were also formed. The bundles of these SWNTs are not uniform and tight, compared to those synthesized by arc discharge or laser ablation. This results in the high BET surface areas, such as 685.2 m 2 /g in the roughly purified sample prepared from Moo.025Coo. 05 Mgo. 925 O, which is higher than that of SWNT samples prepared by laser ablation (285 m 2 /g) [Ye et al . , Appl . Phys . Lett . 74 (1999) 2307] .
  • the tube diameters calculated are in the range of 1.07-1.25 nm.
  • the SWNTs may be predominantly formed through the "base growth” mechanism, in which metal particles responsible for the nanotube nucleation and growth are attached to the support surfaces.
  • the strong interaction between metal particles and support is thus believed to be beneficial to the growth of SWNTs [Su et al . , Chem . Phys . Lett . 322 (2000) 321 ] .
  • the content of molybdenum is elevated too much, it may weaken the interaction between metallic Co and MgO support, and a larger metallic Co particles could easily be formed, leading to the growth of MWNTs.
  • SWNTs were formed over single Fe-based catalysts as revealed by the TEM and Raman spectra shown in Figures 6 and 7.
  • SWNTs were mainly formed with the addition of small amounts of Mo. However, compared with Mo-Co catalysts, more MWNTs were observed over Mo-Fe catalysts.
  • the cost of raw single-walled carbon nanotubes prepared using this catalyst is thus about S$3.8 per gram. After purification, the cost of roughly purification SWNTs is about 7.1 S$/gram. If the Moo.035Coo.07Mgo.895O catalyst is used to produce SWNTs with a little lower quality, such as in example 6, the cost of raw single-walled carbon nanotubes decreases to 2.7 S$/g. After purification, the cost of roughly purified SWNTs lowers to 4S$/g.
  • 300mg of the Moo. 01 Coo.05Mgo. 94 O was placed in the centre of a quartz tube located in a tube furnace.
  • a gas mixture of H 2 and CH 4 with molar ratio of H 2 :CH 4 (4:1) and a total flow rate of 250 cm 3 /min was introduced through mass flowmeters.
  • the furnace temperature was linearly increased up to 1000°C at rate of 5°C/min and held at 1000°C for 2 min.
  • CH 4 was turned off and the sample was cooled down to room temperature in a flow of H 2 .
  • Raw carbon nanotubes were obtained and were purified by immersing them in 150ml of 65% HN0 3 solution. The mixture was stirred for about 8 h to dissolve the catalyst.
  • Example 3 Following the same procedure of Example 2 and using lOg of (Mg (N0 3 ) 2 . 6H 2 0, 0 . 887g of Co (N0 3 ) 2 . 6H 2 0, 0 . 269g of (NH 4 ) 6 M ⁇ 7 ⁇ 2 . 4H 0 and 4g of citric acid and , the Moo . 035 Coo . 0 7 go .89 5 O catalyst was prepared .
  • Example 2 200mg of Moo.025Coo.05Mgo.9 2 5O as prepared in Example 2 was placed in the centre of a horizontal quartz reactor. A gas mixture of H 2 and CH 4 with a molar ratio of H 2 :CH 4 (4:1) and a total flow rate of 250 cm 3 /min was introduced through mass flowmeters. The furnace temperature was linearly increased up to 1000°C at a rate of 5°C/min and held at 1000°C for 2 min. Then CH 4 was turned off and the sample was cooled down in a flow of H 2 . About 0.324g of SWNTs were obtained. Tables 1 and 2 display the results obtained when the process above is carried out with various catalysts.
  • Example 8 Using 200mg of a Moo. 025 Feo. 05 Mgo.925O catalyst and following the same procedure of Example 5, 0.354g of raw single-walled carbon nanotubes were obtained.
  • Example 8 Using 200mg of a Moo. 025 Feo. 05 Mgo.925O catalyst and following the same procedure of Example 5, 0.354g of raw single-walled carbon nanotubes were obtained.

Abstract

La présente invention concerne la synthèse de nanotubes de carbone à paroi unique qui consiste à mettre en contact une matière contenant du carbone avec un catalyseur comprenant au moins deux métaux de transition et un support, au moins un des métaux de transition étant un élément du groupe VIIIB et au moins un des métaux de transition étant un élément du groupe VIB.
PCT/SG2002/000255 2001-10-31 2002-10-30 Synthese a grande echelle de nanotubes de carbone a paroi unique effectuee avec des catalyseurs du groupe viiib potentialises par des metaux du groupe vib WO2003037792A1 (fr)

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WO2004096704A2 (fr) * 2002-07-31 2004-11-11 Carbon Nanotechnologies, Inc. Procede de fabrication de nanotubes de carbone a paroi unique au moyen de catalyseurs supportes
EP1868720A2 (fr) * 2005-02-07 2007-12-26 Hyperion Catalysis International, Inc. Catalyseur à nanotubes de carbone monofeuillets
US7811542B1 (en) 2002-11-26 2010-10-12 Unidym, Inc. Carbon nanotube particulates, compositions and use thereof
BE1019067A3 (nl) * 2008-12-10 2012-02-07 Cheil Ind Inc Metaal nanokatalysator, werkwijze voor het vervaardigen ervan en werkwijze voor het beheersen van de groeitypes koolstof nanobuizen door het gebruik ervan.
WO2014111862A1 (fr) * 2013-01-17 2014-07-24 Saudi Basic Industries Coporation Production de nanotubes de carbone à partir de dioxyde de carbone
EP2873457A4 (fr) * 2012-07-12 2015-07-22 Univ Beijing Catalyseur pour la préparation de nanotubes de carbone monofeuillets sélectivement chiraux et sélectivement conducteurs, son procédé de préparation et son application
CN107343505A (zh) * 2016-05-06 2017-11-14 识骅科技股份有限公司 具二氧化硅纳米粒子及银纳米粒子的纳米碳管复合结构

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Cited By (14)

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Publication number Priority date Publication date Assignee Title
JP2011046611A (ja) * 2002-07-31 2011-03-10 Unidym Inc 担持触媒を用いた単一層カーボンナノチューブの製造方法
WO2004096704A2 (fr) * 2002-07-31 2004-11-11 Carbon Nanotechnologies, Inc. Procede de fabrication de nanotubes de carbone a paroi unique au moyen de catalyseurs supportes
JP2006511437A (ja) * 2002-07-31 2006-04-06 カーボン ナノテクノロジーズ インコーポレーテッド 担持触媒を用いた単一層カーボンナノチューブの製造方法
US7250148B2 (en) 2002-07-31 2007-07-31 Carbon Nanotechnologies, Inc. Method for making single-wall carbon nanotubes using supported catalysts
JP4685454B2 (ja) * 2002-07-31 2011-05-18 ユニダイム、インコーポレイテッド 担持触媒を用いた単一層カーボンナノチューブの製造方法
WO2004096704A3 (fr) * 2002-07-31 2005-11-17 Carbon Nanotechnologies Inc Procede de fabrication de nanotubes de carbone a paroi unique au moyen de catalyseurs supportes
US7811542B1 (en) 2002-11-26 2010-10-12 Unidym, Inc. Carbon nanotube particulates, compositions and use thereof
EP1868720A2 (fr) * 2005-02-07 2007-12-26 Hyperion Catalysis International, Inc. Catalyseur à nanotubes de carbone monofeuillets
EP1868720A4 (fr) * 2005-02-07 2014-07-30 Hyperion Catalysis Int Catalyseur à nanotubes de carbone monofeuillets
BE1019067A3 (nl) * 2008-12-10 2012-02-07 Cheil Ind Inc Metaal nanokatalysator, werkwijze voor het vervaardigen ervan en werkwijze voor het beheersen van de groeitypes koolstof nanobuizen door het gebruik ervan.
EP2873457A4 (fr) * 2012-07-12 2015-07-22 Univ Beijing Catalyseur pour la préparation de nanotubes de carbone monofeuillets sélectivement chiraux et sélectivement conducteurs, son procédé de préparation et son application
WO2014111862A1 (fr) * 2013-01-17 2014-07-24 Saudi Basic Industries Coporation Production de nanotubes de carbone à partir de dioxyde de carbone
CN104936894A (zh) * 2013-01-17 2015-09-23 沙特基础工业公司 源自二氧化碳的碳纳米管生产
CN107343505A (zh) * 2016-05-06 2017-11-14 识骅科技股份有限公司 具二氧化硅纳米粒子及银纳米粒子的纳米碳管复合结构

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