WO1995010481A1 - Nanotubes de carbone et fullerenes imbriques portant des metaux de transition - Google Patents

Nanotubes de carbone et fullerenes imbriques portant des metaux de transition Download PDF

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Publication number
WO1995010481A1
WO1995010481A1 PCT/US1994/011043 US9411043W WO9510481A1 WO 1995010481 A1 WO1995010481 A1 WO 1995010481A1 US 9411043 W US9411043 W US 9411043W WO 9510481 A1 WO9510481 A1 WO 9510481A1
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Prior art keywords
group
metal
composition
transition metal
nested
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PCT/US1994/011043
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English (en)
Inventor
Paul Joseph Fagan
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E.I. Du Pont De Nemours And Company
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Publication of WO1995010481A1 publication Critical patent/WO1995010481A1/fr

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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
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • 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
    • C01B32/152—Fullerenes
    • C01B32/156—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C01B32/162—Preparation characterised by catalysts

Definitions

  • This invention relates to hollow, graphitic tubules of carbon of nanometer dimensions, called nanotubes, and nested fullerenes. Specifically, this invention relates to compositions comprising these nanotubes and nested fullerenes having metals supported thereon, and a method for their preparation.
  • the carbon nanotubes consist of nested concentric tubes of carbon where each tube is made up of curved graphite-like sheets of carbon.
  • the tubes are hollow on the inside and the ends of the tube are usually sealed with fullerene-like caps.
  • the tubes have a high aspect ratio with the diameter being in the range from 2 nanometers to several tens of nanometers and the length being as long as several microns.
  • concentric hollow polygons commonly called nested fullerenes.
  • irradiation with an electron beam can convert nanotubes to concentric hollow spheres.
  • An object of the present invention is to provide sealed and unsealed carbon nanotubes and nested fullerenes with supported transition metal particles, clusters of particles, coatings, or a combination thereof attached to the outside surface of the nanotubes and nested fullerenes.
  • This invention provides a composition comprising at least one. from the group consisting of a carbon nanotube and a nested fullerene, having at least one transition metal supported thereon, said transition metal being selected from the group consisting of: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, , Re, Os, Ir, Pt and Au.
  • reaction product may be heated under vacuum to a temperature from ambient to about 1000°C, driving off any residual metal-complex from the carbon nanotubes and nested fullerenes with metal particles, clusters, and/or coatings attached thereto.
  • FIG. 1A is a photomicrograph of a nanotube with platinum particles, clusters of particles, and a coating supported thereon according to the present invention prior to heat treatment (Example 1) .
  • FIG. IB is a photomicrograph of nanotubes with platinum particles, clusters of particles, and a coating supported thereon according to the present invention after heat treatment (Example 1) .
  • FIG. 2A is a photomicrograph of a nanotube with palladium particles, clusters, and coating supported thereon according to the present invention prior to heat treatment (Example 2) .
  • FIG. 2B is a photomicrograph of a nanotube with palladium particles, clusters, and coating supported thereon according to the present invention after heat treatment (Example 2) .
  • FIG. 3A is a photomicrograph of a nanotube with nickel particles, clusters and coating supported thereon according to the present invention prior to heat treatment (Example 3) .
  • FIG. 3B is a photomicrograph of a nanotube with nickel particles, clusters and coating supported thereon according to the present invention after heat treatment (Example 3) .
  • This invention provides a composition
  • a composition comprising at least one from the group consisting of a carbon nanotube and a nested fullerene, having at least one transition metal supported thereon, said transition metal being selected from the group consisting of: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt and Au.
  • a carbon nanotube comprises a series of hollow, coaxial tubes, wherein each tube is made up of curved graphite-like sheets of carbon of nanometer dimensions.
  • the nanotubes are hollow on the inside and the ends of the nanotube are usually sealed with fullerene-like caps.
  • the dimensions of the nanotube are about 0.1 to 200 nm in diameter and about 1 to 100 microns in length.
  • the carbon nanotube of the present invention can be prepared by the procedure of Ajayan et al. , in “Large- scale synthesis of carbon nanotubes", Nature, 358 (1992) 220-222, incorporated by reference herein.
  • composition of the present invention may comprise nanotubes with sealed or unsealed ends.
  • the ends may be unsealed with chemical methods as reported by Tsang et al., "Thinning and opening of carbon nanotubes by oxidation using carbon dioxide", Nature, 362 (1993) 520-522, wherein the tubes were opened by heating them in carbon dioxide at 850°C.
  • Ajayan et al. opened the tubes by heating them in air above about 700°C, as reported in Nature, 362 (1993) 522-525.
  • a nested fullerene of the present invention comprises a series of hollow, concentric spheres or polyhedra of carbon.
  • Nested fullerenes can be prepared by irradiating a carbon nanotube with an electron beam as reported by Ugarte, Nature, 359 (1992) 708-709.
  • a transition metal is supported by the carbon nanotube and/or nested fullerene of the present invention.
  • the transition metal is selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt and Au.
  • the transition metal is selected from the group consisting of: Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag and Au; more preferably, Co, Rh, Ir, Ni, Pd and Pt; most preferably, Ni, Pd and Pt .
  • At least one transition metal is supported on the nanotube and/or nested fullerene.
  • the transition metal may be in the form of individual metal particles, clusters of metal particles, a coating, or a combination thereof. The particles and clusters range in size from about 0.8 to 20 nm in size, and the coatings are generally less than about 30 A thick.
  • the term "supported” shall mean that the transition metal is attached to the outside surface of the nanotube and/or nested fullerene with the transition metal in the form of particles, clusters of particles, and/or a coating. Since the carbon nanotubes and nested fullerenes have curved carbon surfaces, deposition of metals on these materials results in a unique form of metal on carbon.
  • This invention also provides a process for the preparation of a composition
  • a composition comprising at least one from the group consisting of a carbon nanotube and a nested fullerene, having at least one transition metal supported thereon, said transition metal from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt and Au.
  • the transition metal is Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag and Au; more preferably, Co, Rh, Ir, Ni, Pd and Pt; and most preferably, Ni, Pd and Pt .
  • the reaction takes place by slurrying the carbon nanotube and/or nested fullerene with the metal-complex in an inert solvent. Suitable inert solvents are unreactive towards the metal complex.
  • Non-polar hydrocarbons such as alkanes, e.g., hexane, and aromatics, e.g., benzene and toluene, are preferred.
  • Suitable metal ligands are characterized by being labile, that is they are removed upon heating.
  • organics that are volatile in the temperature range of 25°C to 500°C suitable as a metal ligand are ethylene, ammonia, cyclopentadienyl, cyclooctadiene (C ⁇ Hig) and triethylphosphine ((C 2 Hs)3P) . Cyclooctadiene and triethylphosphine are preferred.
  • the material is isolated by filtering, centrifuging or decanting and washed with an inert solvent, as described above, to remove excess metal-complex. Examination by high resolution transmission electron microscopy at this stage in the process shows a material with an amorphous coating of the metal and some remaining ligands. Heating this material in vacuo from ambient to about 1000°C, preferably, about 300°C to 400°C drives off any residual metal-complex ligand, producing the carbon nanotube and/or nested fullerene with metal particles, clusters of particles and/or coatings attached. The resulting particles and clusters range from about 0.8 to 20 nm in size, and the coatings are generally less than about 30 A thick.
  • Suitable inert solvents are unreactive towards the metal complex.
  • Non-polar hydrocarbons such as alkanes, e.g., hexane, and aromatics, e.g., benzene and toluene, are preferred.
  • the reaction product After isolating the reaction product by filtering, centrifuging or decanting, the reaction product is washed with an inert solvent, as described above, to remove excess metal-complex.
  • the reaction product may be heated under vaccuum to a temperature from ambient to about 1000°C, preferably about 300°C to 400°C, to form the transition metal supported composition.
  • compositions of the present invention in which metal is supported on a curved surface are useful as catalysts in chemical reactions such as hydrogenation of organic substrates, for example, hydrogenation of diphenylacetylene to cis-stilbene and trans-stilbene.
  • Other uses for compositions of the present invention comprise catalyzing reactions, such as dehydrohalogenation, hydrocarbon cracking, and dehydrogenation; fragmentation reactions, such as decarbonylation and decarboxamidation; and isomerization reactions.
  • EXAMPLE 1 A mixture of carbon nanotubes and nested fullerenes, purchased from Terra Simco Company,
  • the resulting material is made up of carbon nanotubes and nested fullerenes having 10-80 A platinum clusters attached to the outer surface in some regions. along with regions coated with a layer or layers of platinum metal as shown in Fig. IB.
  • a mixture of carbon nanotubes and nested fullerenes purchased from Terra Simco Company,
  • the resulting material is made up of carbon nanotubes and nested fullerenes having 10-80 A palladium clusters attached to the outer surface in some regions, along with regions coated with a layer or layers of palladium metal.
  • EXAMPLE 3 A mixture of carbon nanotubes and nested fullerenes, purchased from Terra Simco Company,
  • EXAMPLE 4 A Fisher-Porter bottle was charged with 0.200 g of a mixture of carbon nanotubes and nested fullerenes, purchased commercially from Terra Simco Company,

Abstract

L'invention décrit une composition qui comprend un nanotube de carbone et/ou un fullerène imbriqué portant des particules, amas et/ou revêtements de métaux de transition, ainsi qu'un procédé pour la préparation de ceux-ci. Le métal est de préférence compris dans le groupe : Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag et Au.
PCT/US1994/011043 1993-10-13 1994-10-06 Nanotubes de carbone et fullerenes imbriques portant des metaux de transition WO1995010481A1 (fr)

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US13570293A 1993-10-13 1993-10-13
US08/135,702 1993-10-13

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0796403A1 (fr) * 1994-12-08 1997-09-24 Hyperion Catalysis International, Inc. Nanotubes rendus fonctionnels
WO1997036856A1 (fr) * 1996-04-02 1997-10-09 E.I. Du Pont De Nemours And Company Isomerisation en phase vapeur catalysee de 2-alkyl-3-monoalcenenitriles non conjugues
WO1998009725A1 (fr) * 1996-09-06 1998-03-12 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Catalyseur et son procede de production
WO1999065821A1 (fr) * 1998-06-19 1999-12-23 The Research Foundation Of State University Of New York Nanotubes de carbone autonomes alignes et leur synthese
WO2000009443A1 (fr) * 1998-08-14 2000-02-24 The Board Of Trustees Of The Leland Stanford Junior University Structures de nanotubes en carbone fabriquees au moyen d'ilots catalyseurs
DE10048406A1 (de) * 2000-09-29 2002-06-06 Infineon Technologies Ag Verfahren zum Herstellen eines heterogenen Katalysators; dadurch hergestellter, heterogener Katalysator; sowie Verwendung des hergestellten heterogenen Katalysators zum Umsetzen eines Substrats
WO2003072679A1 (fr) * 2002-02-22 2003-09-04 Carbon Nanotechnologies, Inc. Matieres de gestion thermique au niveau moleculaire renfermant des nanotubes de carbone a paroi unique
US6653509B2 (en) 1996-09-06 2003-11-25 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Method for the liquid-phase hydrogenation of organic materials
WO2005007288A1 (fr) * 2003-07-10 2005-01-27 Obschestvo S Ogranichennoi Otvetstvennostju 'fiztekhpribor' Procede de production d'un catalyseur d'hydrogenation contenant du palladium
US6887453B2 (en) 2002-08-24 2005-05-03 Haldor Topsoe A/S Rhenium (IV) sulphide nanotube material and method of preparation
US7022541B1 (en) 2001-11-19 2006-04-04 The Board Of Trustees Of The Leland Stanford Junior University Patterned growth of single-walled carbon nanotubes from elevated wafer structures
US7183228B1 (en) 2001-11-01 2007-02-27 The Board Of Trustees Of The Leland Stanford Junior University Carbon nanotube growth
EP1782885A1 (fr) 2005-11-07 2007-05-09 Research Institute of Petroleum Industry (RIPI) Catalyseur à base de cobalt sur support en nanotubes de carbone pour transformer un gaz de synthèse en hydrocarbures
US7235159B2 (en) 2003-09-17 2007-06-26 Molecular Nanosystems, Inc. Methods for producing and using catalytic substrates for carbon nanotube growth
DE102004027865B4 (de) * 2003-06-13 2007-09-13 Korea Advanced Institute Of Science & Technology Leitende Kohlenstoff-Nanotubes, dotiert mit einem Metall, und Verfahren zur Herstellung eines Biosensors, der diese benutzt
WO2007134722A1 (fr) * 2006-05-23 2007-11-29 Bayer Materialscience Ag Catalyseur stable à la température pour l'oxydation en phase gazeuse
GB2463046A (en) * 2008-08-29 2010-03-03 Univ Surrey Metal complexes comprising a fullerite
WO2010142350A1 (fr) * 2009-06-12 2010-12-16 Aggregate Energy, Llc. Catalyseur comprenant un métal et un composant complémentaire et procédé pour l'hydrogénation de produits organiques contenant de l'oxygène
EP2514524A1 (fr) * 2011-04-21 2012-10-24 Research Institute of Petroleum Industry (RIPI) Nanocatalyseur et procédé pour l'élimination de composés du soufre présents dans des hydrocarbures
CN104084227A (zh) * 2014-06-26 2014-10-08 上海第二工业大学 一种煤直接液化催化添加剂、制备方法及其应用
US9406985B2 (en) 2009-01-13 2016-08-02 Nokia Technologies Oy High efficiency energy conversion and storage systems using carbon nanostructured materials
WO2018046037A1 (fr) * 2016-09-09 2018-03-15 Technische Universität Darmstadt Détection olfactive du monoxyde de carbone
CN108558084A (zh) * 2018-06-13 2018-09-21 江苏湖大化工科技有限公司 一种高盐废水中有机物电解催化耦合高级氧化的处理方法及装置

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Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0796403A1 (fr) * 1994-12-08 1997-09-24 Hyperion Catalysis International, Inc. Nanotubes rendus fonctionnels
US7854945B2 (en) 1994-12-08 2010-12-21 Hyperion Catalysis International, Inc. Functionalized nanotubes
EP0796403A4 (fr) * 1994-12-08 1998-04-22 Hyperion Catalysis Int Nanotubes rendus fonctionnels
WO1997036856A1 (fr) * 1996-04-02 1997-10-09 E.I. Du Pont De Nemours And Company Isomerisation en phase vapeur catalysee de 2-alkyl-3-monoalcenenitriles non conjugues
US6653509B2 (en) 1996-09-06 2003-11-25 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Method for the liquid-phase hydrogenation of organic materials
WO1998009725A1 (fr) * 1996-09-06 1998-03-12 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Catalyseur et son procede de production
WO1999065821A1 (fr) * 1998-06-19 1999-12-23 The Research Foundation Of State University Of New York Nanotubes de carbone autonomes alignes et leur synthese
US6863942B2 (en) 1998-06-19 2005-03-08 The Research Foundation Of State University Of New York Free-standing and aligned carbon nanotubes and synthesis thereof
WO2000009443A1 (fr) * 1998-08-14 2000-02-24 The Board Of Trustees Of The Leland Stanford Junior University Structures de nanotubes en carbone fabriquees au moyen d'ilots catalyseurs
US6346189B1 (en) 1998-08-14 2002-02-12 The Board Of Trustees Of The Leland Stanford Junior University Carbon nanotube structures made using catalyst islands
US7166325B2 (en) 1998-08-14 2007-01-23 The Board Of Trustees Of The Leland Stanford Junior University Carbon nanotube devices
DE10048406A1 (de) * 2000-09-29 2002-06-06 Infineon Technologies Ag Verfahren zum Herstellen eines heterogenen Katalysators; dadurch hergestellter, heterogener Katalysator; sowie Verwendung des hergestellten heterogenen Katalysators zum Umsetzen eines Substrats
US7183228B1 (en) 2001-11-01 2007-02-27 The Board Of Trustees Of The Leland Stanford Junior University Carbon nanotube growth
US7022541B1 (en) 2001-11-19 2006-04-04 The Board Of Trustees Of The Leland Stanford Junior University Patterned growth of single-walled carbon nanotubes from elevated wafer structures
WO2003072679A1 (fr) * 2002-02-22 2003-09-04 Carbon Nanotechnologies, Inc. Matieres de gestion thermique au niveau moleculaire renfermant des nanotubes de carbone a paroi unique
US6887453B2 (en) 2002-08-24 2005-05-03 Haldor Topsoe A/S Rhenium (IV) sulphide nanotube material and method of preparation
DE102004027865B4 (de) * 2003-06-13 2007-09-13 Korea Advanced Institute Of Science & Technology Leitende Kohlenstoff-Nanotubes, dotiert mit einem Metall, und Verfahren zur Herstellung eines Biosensors, der diese benutzt
KR100851725B1 (ko) * 2003-07-10 2008-08-11 오브스체스트보 에스 오그라니체노이 오트베트스트베노스트주 "피즈테크프리보르" 팔라듐 함유 수소화 촉매의 제조 방법
US7465689B2 (en) * 2003-07-10 2008-12-16 Valery Borisovich Ukraintsev Method for producing a palladium-containing hydrogenation catalyst
WO2005007288A1 (fr) * 2003-07-10 2005-01-27 Obschestvo S Ogranichennoi Otvetstvennostju 'fiztekhpribor' Procede de production d'un catalyseur d'hydrogenation contenant du palladium
US7235159B2 (en) 2003-09-17 2007-06-26 Molecular Nanosystems, Inc. Methods for producing and using catalytic substrates for carbon nanotube growth
EP1782885A1 (fr) 2005-11-07 2007-05-09 Research Institute of Petroleum Industry (RIPI) Catalyseur à base de cobalt sur support en nanotubes de carbone pour transformer un gaz de synthèse en hydrocarbures
WO2007134722A1 (fr) * 2006-05-23 2007-11-29 Bayer Materialscience Ag Catalyseur stable à la température pour l'oxydation en phase gazeuse
GB2463046A (en) * 2008-08-29 2010-03-03 Univ Surrey Metal complexes comprising a fullerite
US9406985B2 (en) 2009-01-13 2016-08-02 Nokia Technologies Oy High efficiency energy conversion and storage systems using carbon nanostructured materials
WO2010142350A1 (fr) * 2009-06-12 2010-12-16 Aggregate Energy, Llc. Catalyseur comprenant un métal et un composant complémentaire et procédé pour l'hydrogénation de produits organiques contenant de l'oxygène
US8389781B2 (en) 2009-06-12 2013-03-05 Aggregate Energy, Llc Catalyst with supplement component for hydroprocessing of bio-feedstock
EP2514524A1 (fr) * 2011-04-21 2012-10-24 Research Institute of Petroleum Industry (RIPI) Nanocatalyseur et procédé pour l'élimination de composés du soufre présents dans des hydrocarbures
CN104084227A (zh) * 2014-06-26 2014-10-08 上海第二工业大学 一种煤直接液化催化添加剂、制备方法及其应用
WO2018046037A1 (fr) * 2016-09-09 2018-03-15 Technische Universität Darmstadt Détection olfactive du monoxyde de carbone
CN108558084A (zh) * 2018-06-13 2018-09-21 江苏湖大化工科技有限公司 一种高盐废水中有机物电解催化耦合高级氧化的处理方法及装置
CN108558084B (zh) * 2018-06-13 2024-01-23 江苏湖大化工科技有限公司 一种高盐废水中有机物电解催化耦合高级氧化的处理方法及装置

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