WO2003018474A1 - Synthese de nanostructures - Google Patents

Synthese de nanostructures Download PDF

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Publication number
WO2003018474A1
WO2003018474A1 PCT/GB2002/003670 GB0203670W WO03018474A1 WO 2003018474 A1 WO2003018474 A1 WO 2003018474A1 GB 0203670 W GB0203670 W GB 0203670W WO 03018474 A1 WO03018474 A1 WO 03018474A1
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WO
WIPO (PCT)
Prior art keywords
stainless steel
process according
catalyst
carbon
flake
Prior art date
Application number
PCT/GB2002/003670
Other languages
English (en)
Inventor
Elodie Berangere Fourre
Virginie Ogrodnik
Allin Sidney Pratt
Original Assignee
Johnson Matthey Public Limited Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Johnson Matthey Public Limited Company filed Critical Johnson Matthey Public Limited Company
Publication of WO2003018474A1 publication Critical patent/WO2003018474A1/fr

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0021Carbon, e.g. active carbon, carbon nanotubes, fullerenes; Treatment thereof
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/158Carbon nanotubes
    • C01B32/16Preparation
    • C01B32/162Preparation characterised by catalysts
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/32Hydrogen storage

Definitions

  • the present invention relates to processes for the synthesis of carbon nanostructures.
  • Carbon nanostructures are fullerene-type structures and typically have at least one dimension in the nanometre range. They may be, but are not limited to, tubular structures, fibres, powders or a mixture of these morphologies. In all these structures the basic building blocks of the structure are six and five-membered carbon rings, joined in various configurations. Carbon nanotubes were first reported by Iijima (Nature 354, (1991), 56). They have a tubular structure, and may be single- walled or multi- walled. Fibres may or may not be hollow, and the basal graphitic plane may be oriented along the length of the fibre or across the fibre, and even stacked conically. Many of the nanostructures and the factors controlling their formation and properties are discussed by Harris (Carbon Nanostructures and Related Structures, Cambridge 1999) and Dresselhaus et al (Science of Fullerenes and Carbon Nanotubes, Academic, 1996).
  • Carbon nanostructures can be synthesised by methods such as arc discharge, laser ablation and chemical vapour deposition (CVD). Many of the synthetic methods use a catalyst to promote the growth of the nanostructures. In CVD methods, a carbonaceous gas such as C H 2 , CH 4 , or CO is decomposed by a catalyst. The synthesis of nanostructures by CVD methods is a promising mass production method because the temperature required for nanostructure growth is around 700°C, which is much lower than in arc discharge or laser ablation. Takiwara et al (Jpn. J. appl. Phys. Vol. 39 (2000), 5177-5179) disclose a CVD method that uses nickel and zinc deposited on copper substrates to produce carbon "nanocoils".
  • Li et al. disclose a CVD method for the controlled growth of carbon nanotubes wherein the catalyst comprises graphite foil coated with a stainless steel film.
  • the film is applied using magnetron sputtering and is 2-lOOnm thick. Annealing in hydrogen converts the stainless steel film to stainless steel particles.
  • a process for the synthesis of carbon nanostructures comprises contacting a carbon source with a catalyst such that carbon nanostructures are grown on the catalyst, characterised in that the catalyst comprises stainless steel flake.
  • the term "catalyst” is used to describe a finely divided material on which reactions can take place and where nucleation and growth can proceed. It is not intended that the term 'catalyst' be solely used in the conventional sense, that is, there is no requirement in the present invention that the catalyst be unchanged during the process of the invention.
  • the term "stainless steel flake” is used to describe an iron alloy in particulate form where the particles have one physical dimension (minor dimension) which is substantially smaller than the other two physical dimensions.
  • the flake suitably has a minor dimension (or thickness) of 0.1 -1 ⁇ m, preferably about 0.6 ⁇ m.
  • stainless steels are those alloy steels which include appreciable amounts of chromium, for example 12% and above. Typically, the alloys may contain up to 25% chromium, up to 15% nickel, up to 1.5% carbon, and small amounts of other elements such as niobium, titanium, aluminium and copper, with the balance being iron.
  • a preferred composition the stainless steel flake is designated 316L, which is a common grade of stainless steel of low carbon content. Alternative designations of stainless steel may also be used as can mixtures of two or more types of stainless steel. Suitable 316L stainless steel can be purchased from Novamet Speciality Products Corporation in the form of flakes with a minor dimension of ca. 0.6 ⁇ m, the other two dimensions of the flake being in the range 10- 100 ⁇ m.
  • the carbon source comprises a carbonaceous gas, a carbonaceous liquid or any mixture thereof.
  • Some non-limiting examples include carbon monoxide, methane, natural gas and other gaseous or liquid hydrocarbons.
  • the carbon source may be provided substantially pure or be diluted or admixed with an inert or reactive carrier.
  • a first method a small quantity of stainless steel flake is placed in a tube, preferably a quartz tube. The tube is rotated to distribute the flake on the surface of the tube. The quantity of stainless steel flake used will depend on factors such as the size and shape of the tube and the gas flow rate.
  • a carbon source gas e.g., CO, CH 4 or similar hydrocarbon is passed over the flake at temperatures between 475°C and 1000°C and carbon nanostructures are grown on the flake.
  • the reaction time is dependant on gas flow rate and temperature.
  • the carbon source gas is diluted with hydrogen.
  • the stainless steel flake is fluidised in fluidised bed system.
  • a carbon source gas and optionally hydrogen are passed into the bed.
  • the carbon nanostructures grow on the flake. It is possible that some of the nanostructures may become detached from the flake during the reaction and be contained within the gas flow from the bed.
  • the stainless steel flake is admixed with a carbonaceous liquid and the mixture contacted with a heat source.
  • the flake may be blended into an organic liquid such as xylene, and sprayed into the hot zone of a furnace.
  • the organic liquid acts as a carbon source so it is not necessary to add a carbon source gas.
  • the process of the present invention may be carried out under substantially atmospheric pressure. This simplifies the process and leads to further cost reductions when compared to e.g. CVD methods for nano-structure synthesis. Although not as preferred, high and low pressures can also be used if desired.
  • the stainless steel flake is supported on a support.
  • the supported stainless steel catalyst as reported by Li et al is produced by sputtering commercial stainless steel onto a graphite foil substrate.
  • stainless steel flake can be deposited on a support by simply bringing the flake into contact with the support.
  • the support may be a heat resistant support such as a honeycomb support made of, for example, cordierite.
  • the heat resistant support may be a heat exchanger, which may be made of surface oxidised metal or high temperature plastic. If nanostructures are grown on the stainless steel flake deposited on the support, then the support may be a useful hydrogen storage device. Therefore the present invention also provides a process for producing a hydrogen storage device comprising the steps of depositing stainless steel flake on a support and synthesising carbon nanostructures on the flake.
  • Stainless steel is supplied to the process of the invention as stainless steel flake.
  • the form of the stainless steel will change during the process and the catalyst may not actually be stainless steel in the form of the original flakes, but may be stainless steel in a different form. Some change of shape is likely to occur particularly at more elevated temperatures during processing as the flake reduces its surface energy.
  • the carbon nanostructures grow on the surface of the stainless steel catalyst. Depending on the intended application of the carbon nanostructures, it may be necessary to remove the nanostructures from the catalyst.
  • One suitable method for the removal of the nanostructures from the catalyst is boiling in hydrochloric acid, although other methods will be apparent to those skilled in the art. For most applications however, it is unlikely to be necessary to remove the nanostructures from the catalyst.
  • Stainless steel is inert in many chemical environments, so the presence of stainless steel is unlikely to interfere with the functioning of the nanostructures.
  • the present invention provides carbon nanostructures as produced by the novel process according to the invention.
  • the present invention provides the use of carbon nanostructures as produced by the novel process according to the invention, as hydrogen storage media.
  • 0.020g of 316L stainless steel flake from Novamet Speciality Products Corporation (0.6 ⁇ m thick, other dimensions 40-100 ⁇ m) was placed in a quartz tube. The tube was rotated to distribute the flake on the surface of the tube. The tube was heated to a temperature of between 475°C and 800°C and a gas mixture of a carbon source and hydrogen was passed through the tube at a flow rate of approximately 600ml per hour for 24 hours (unless otherwise stated). At the end of this period the tube was cooled first under hydrogen and then under nitrogen.

Abstract

L'invention se rapporte à un procédé de synthèse de nanostructures de carbone. Un catalyseur est utilisé pour favoriser la croissance des nanostructures à partir d'une source de carbone, caractérisé en ce qu'un flocon en acier inoxydable est utilisé pour produire le catalyseur.
PCT/GB2002/003670 2001-08-22 2002-08-09 Synthese de nanostructures WO2003018474A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0120366.0 2001-08-22
GBGB0120366.0A GB0120366D0 (en) 2001-08-22 2001-08-22 Nanostructure synthesis

Publications (1)

Publication Number Publication Date
WO2003018474A1 true WO2003018474A1 (fr) 2003-03-06

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GB (1) GB0120366D0 (fr)
WO (1) WO2003018474A1 (fr)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2399092A (en) * 2003-03-03 2004-09-08 Morgan Crucible Co Nanotube and/or nanofibre synthesis
WO2008128437A1 (fr) * 2007-04-18 2008-10-30 Tsinghua University Réacteurs multi-étages pour la production continue de nanotubes de carbone
JP2015520717A (ja) * 2012-04-16 2015-07-23 シーアストーン リミテッド ライアビリティ カンパニー 炭素酸化物触媒変換器中で金属触媒を使用するための方法
US9090472B2 (en) 2012-04-16 2015-07-28 Seerstone Llc Methods for producing solid carbon by reducing carbon dioxide
US9221685B2 (en) 2012-04-16 2015-12-29 Seerstone Llc Methods of capturing and sequestering carbon
US9556031B2 (en) 2009-04-17 2017-01-31 Seerstone Llc Method for producing solid carbon by reducing carbon oxides
US9586823B2 (en) 2013-03-15 2017-03-07 Seerstone Llc Systems for producing solid carbon by reducing carbon oxides
US9598286B2 (en) 2012-07-13 2017-03-21 Seerstone Llc Methods and systems for forming ammonia and solid carbon products
US9604848B2 (en) 2012-07-12 2017-03-28 Seerstone Llc Solid carbon products comprising carbon nanotubes and methods of forming same
US9650251B2 (en) 2012-11-29 2017-05-16 Seerstone Llc Reactors and methods for producing solid carbon materials
US9731970B2 (en) 2012-04-16 2017-08-15 Seerstone Llc Methods and systems for thermal energy recovery from production of solid carbon materials by reducing carbon oxides
US9779845B2 (en) 2012-07-18 2017-10-03 Seerstone Llc Primary voltaic sources including nanofiber Schottky barrier arrays and methods of forming same
US9783416B2 (en) 2013-03-15 2017-10-10 Seerstone Llc Methods of producing hydrogen and solid carbon
US9796591B2 (en) 2012-04-16 2017-10-24 Seerstone Llc Methods for reducing carbon oxides with non ferrous catalysts and forming solid carbon products
US9896341B2 (en) 2012-04-23 2018-02-20 Seerstone Llc Methods of forming carbon nanotubes having a bimodal size distribution
US10086349B2 (en) 2013-03-15 2018-10-02 Seerstone Llc Reactors, systems, and methods for forming solid products
US10106416B2 (en) 2012-04-16 2018-10-23 Seerstone Llc Methods for treating an offgas containing carbon oxides
US10115844B2 (en) 2013-03-15 2018-10-30 Seerstone Llc Electrodes comprising nanostructured carbon
US10815124B2 (en) 2012-07-12 2020-10-27 Seerstone Llc Solid carbon products comprising carbon nanotubes and methods of forming same
WO2021168246A1 (fr) * 2020-02-19 2021-08-26 Northeastern University Génération de rendements élevés de nanotubes de carbone (ntc) à l'aide de catalyseurs métalliques recyclés
US11752459B2 (en) 2016-07-28 2023-09-12 Seerstone Llc Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
ARAKI H ET AL: "Effects of substrate materials on growth of carbon nanotubes by chemical vapor deposition using metal-phthalocyanines", JAPANESE JOURNAL OF APPLIED PHYSICS, PART 2 (LETTERS), 15 NOV. 1999, PUBLICATION OFFICE, JAPANESE JOURNAL APPL. PHYS, JAPAN, vol. 38, no. 11B, pages L1351 - L1353, XP001092760, ISSN: 0021-4922 *
LI W Z ET AL: "Controlled growth of carbon nanotubes on graphite foil by chemical vapor deposition", CHEMICAL PHYSICS LETTERS, 23 FEB. 2001, ELSEVIER, NETHERLANDS, vol. 335, no. 3-4, pages 141 - 149, XP002217825, ISSN: 0009-2614 *
LIMING YUAN ET AL: "Ethylene flame synthesis of well-aligned multi-walled carbon nanotubes", CHEMICAL PHYSICS LETTERS, 28 SEPT. 2001, ELSEVIER, NETHERLANDS, vol. 346, no. 1-2, pages 23 - 28, XP002219496, ISSN: 0009-2614 *
SONEDA Y ET AL: "Formation and texture of carbon nanofilaments by the catalytic decomposition of CO on stainless-steel plate", CARBON, ELSEVIER SCIENCE PUBLISHING, NEW YORK, NY, US, vol. 38, no. 3, 2000, pages 478 - 480, XP004186295, ISSN: 0008-6223 *

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2399092B (en) * 2003-03-03 2005-02-16 Morgan Crucible Co Nanotube and/or nanofibre synthesis
GB2399092A (en) * 2003-03-03 2004-09-08 Morgan Crucible Co Nanotube and/or nanofibre synthesis
WO2008128437A1 (fr) * 2007-04-18 2008-10-30 Tsinghua University Réacteurs multi-étages pour la production continue de nanotubes de carbone
US9556031B2 (en) 2009-04-17 2017-01-31 Seerstone Llc Method for producing solid carbon by reducing carbon oxides
US9090472B2 (en) 2012-04-16 2015-07-28 Seerstone Llc Methods for producing solid carbon by reducing carbon dioxide
US9731970B2 (en) 2012-04-16 2017-08-15 Seerstone Llc Methods and systems for thermal energy recovery from production of solid carbon materials by reducing carbon oxides
US9221685B2 (en) 2012-04-16 2015-12-29 Seerstone Llc Methods of capturing and sequestering carbon
US10106416B2 (en) 2012-04-16 2018-10-23 Seerstone Llc Methods for treating an offgas containing carbon oxides
EP2838841A4 (fr) * 2012-04-16 2015-12-23 Seerstone Llc Procédés d'utilisation de catalyseurs métalliques dans les convertisseurs catalytiques d'oxyde de carbone
US9796591B2 (en) 2012-04-16 2017-10-24 Seerstone Llc Methods for reducing carbon oxides with non ferrous catalysts and forming solid carbon products
US9637382B2 (en) 2012-04-16 2017-05-02 Seerstone Llc Methods for producing solid carbon by reducing carbon dioxide
JP2015520717A (ja) * 2012-04-16 2015-07-23 シーアストーン リミテッド ライアビリティ カンパニー 炭素酸化物触媒変換器中で金属触媒を使用するための方法
US9896341B2 (en) 2012-04-23 2018-02-20 Seerstone Llc Methods of forming carbon nanotubes having a bimodal size distribution
US10815124B2 (en) 2012-07-12 2020-10-27 Seerstone Llc Solid carbon products comprising carbon nanotubes and methods of forming same
US9604848B2 (en) 2012-07-12 2017-03-28 Seerstone Llc Solid carbon products comprising carbon nanotubes and methods of forming same
US10358346B2 (en) 2012-07-13 2019-07-23 Seerstone Llc Methods and systems for forming ammonia and solid carbon products
US9598286B2 (en) 2012-07-13 2017-03-21 Seerstone Llc Methods and systems for forming ammonia and solid carbon products
US9779845B2 (en) 2012-07-18 2017-10-03 Seerstone Llc Primary voltaic sources including nanofiber Schottky barrier arrays and methods of forming same
US9650251B2 (en) 2012-11-29 2017-05-16 Seerstone Llc Reactors and methods for producing solid carbon materials
US10086349B2 (en) 2013-03-15 2018-10-02 Seerstone Llc Reactors, systems, and methods for forming solid products
US10115844B2 (en) 2013-03-15 2018-10-30 Seerstone Llc Electrodes comprising nanostructured carbon
US9783416B2 (en) 2013-03-15 2017-10-10 Seerstone Llc Methods of producing hydrogen and solid carbon
US9586823B2 (en) 2013-03-15 2017-03-07 Seerstone Llc Systems for producing solid carbon by reducing carbon oxides
US11752459B2 (en) 2016-07-28 2023-09-12 Seerstone Llc Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same
US11951428B2 (en) 2016-07-28 2024-04-09 Seerstone, Llc Solid carbon products comprising compressed carbon nanotubes in a container and methods of forming same
WO2021168246A1 (fr) * 2020-02-19 2021-08-26 Northeastern University Génération de rendements élevés de nanotubes de carbone (ntc) à l'aide de catalyseurs métalliques recyclés

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