WO2002020401A1 - Nanofibres de graphite cristallin et procede de production correspondant - Google Patents

Nanofibres de graphite cristallin et procede de production correspondant Download PDF

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Publication number
WO2002020401A1
WO2002020401A1 PCT/US2001/028199 US0128199W WO0220401A1 WO 2002020401 A1 WO2002020401 A1 WO 2002020401A1 US 0128199 W US0128199 W US 0128199W WO 0220401 A1 WO0220401 A1 WO 0220401A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon
nanofibers
nanofiber
catalyst
iron
Prior art date
Application number
PCT/US2001/028199
Other languages
English (en)
Inventor
R. Terry K. Baker
Nelly M Rodriguez
Original Assignee
Catalytic Materials Ltd
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
Priority claimed from US09/659,441 external-priority patent/US6537515B1/en
Application filed by Catalytic Materials Ltd filed Critical Catalytic Materials Ltd
Priority to CA002420004A priority Critical patent/CA2420004A1/fr
Priority to EP01968718A priority patent/EP1349808A4/fr
Publication of WO2002020401A1 publication Critical patent/WO2002020401A1/fr

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Classifications

    • 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
    • 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
    • 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
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
    • D01F9/1278—Carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]

Definitions

  • This invention relates to a process for producing substantially crystalline graphitic carbon nanofibers comprised of graphite sheets.
  • the graphite sheets are substantially parallel or substantially perpendicular to the longitudinal axis of the carbon nanofiber.
  • these carbon nanofibers are produced by contacting an iron, or an iron:copper, or an iron: nickel bimetallic bulk catalyst with a mixture of carbon monoxide and hydrogen at temperatures from about 670°C to about 725°C for an effective amount of time.
  • the nanofibers are produced by use of an iron:copper bimetallic bulk catalyst at temperatures from about 550°C to about 670°C.
  • Nanostructure materials are quickly gaining importance for various potential commercial applications. Such applications include their use to store molecular hydrogen, serve as catalyst supports, as reinforcing components for polymeric composites, and to be useful in various batteries.
  • Carbon nanostructure materials are typically prepared from the decomposition of carbon-containing gases over selected catalytic metal surfaces at temperatures ranging from about 500° to about 1,200°C.
  • U.S. Patent Nos. 5,149,584 and 5,618,875 to Baker et al. teach carbon nanofibers as reinforcing components in polymer reinforced composites.
  • the carbon nanofibers can either be used as is, or as part of a structure comprised of carbon fibers having carbon nanofibers grown therefrom.
  • the examples of these patents show the preparation of various carbon nanostructures by the decomposition of a mixture of ethylene and hydrogen in the presence of metal catalysts, such as iron, nickel, a nickel:copper alloy, an iron:copper alloy, etc.
  • U.S. Patent No. 5,413,866 to Baker et al. teaches carbon nanostructures
  • These carbon nanostructures are taught as being prepared by depositing a catalyst containing at least one Group IB metal and at least one other metal, on a suitable refractory support and then subjecting the catalyst-treated support to a carbon- containing gas at a temperature from the decomposition temperature of the carbon- containing gas to the deactivation temperature of the catalyst.
  • U.S. Patent No. 5,458,784 also to Baker et al. teaches the use of the carbon nanostructures of U.S. Patent No. 5,413,866 for removing contaminants from aqueous and gaseous steams; and U.S. Patent No. 5,653,951 to Rodriguez et al. discloses and claims that molecular hydrogen can be stored in layered nanostructure materials having specific distances between layers.
  • the examples of these patents teach the aforementioned preparation methods, as well as the decomposition of a mixture of carbon monoxide and hydrogen in the presence of an iron powder catalyst at 600°C. All of the above referenced US patents are incorporated herein by reference.
  • substantially crystalline graphitic carbon nanofibers comprised of graphite sheets that are substantially parallel or substantially perpendicular to the longitudinal axis of the nanofibers, wherein the distance between graphite sheets is from about 0.335 nm to about 0.67 nm, and having a crystallinity greater than about 95%. In a preferred embodiment the distance between the graphite sheets is from about 0.335 and 0.40 nm.
  • a process for producing substantially crystalline graphitic carbon nanofibers having graphite sheets substantially parallel to the longitudinal axis of the nanofibers comprises reacting a mixture of CO/H in the presence of a bulk powder catalyst comprised of Fe, Fe:Cu bimetallic, or Fe ' :Ni bimetallic for an effective amount of time at a temperature from about 670°C to about 725°C.
  • a process of producing substantially crystalline graphitic carbon nanofibers having graphite sheets substantially perpendicular to the longitudinal axis of the nanofiber comprises reacting a mixture of CO H 2 in the presence of a powder Fe:Cu bimetallic catalyst for an effective amount of time at a temperature from about 550°C to about 670°C.
  • the catalyst is an Fe:Cu bimetallic catalyst wherein the ratio of Fe to Cu is from about 5:95 to about 95:5 and the ratio of CO to H 2 is from about 95:5 to about 5:95, preferably from about 80:20 to about 20:80.
  • the carbon nanofibers of the present invention possess can two distinct novel structures. One in which graphite sheets, constituting the nanostructure, are aligned in a direction that is substantially parallel to the growth axis (longitudinal axis) of the nanofiber, and the other wherein the graphite sheets are aligned substantially perpendicular to the longitudinal, or growth, axis.
  • the carbon nanofibers having their graphite substantially parallel are sometimes referred to herein as "ribbon” structures and those having their graphite sheets substantially perpendicular are sometimes referred to herein as "platelet” structures.
  • the carbon nanostructures of the present invention are distinguished from the so-call “fibrils" or cylindrical carbon nanostructures.
  • the graphite sheets that compose the nanostructures of the present invention are either discontinuous sheets or faceted flat structures.
  • Cylindrical carbon nanostructures are composed of continous, or tubular, graphite sheets and can be represented by a tube within a tube structure with a hollow center.
  • the carbon nanofibers of the present invention have a unique set of properties, which include: (i) a nitrogen surface area from about 40 to 120 m 2 /g; (ii) an electrical resistivity of 0.4 ohm*cm to 0.1 ohm»cm; (iii) a crystallinity from about 95% to 100%; and (iv) a spacing between adjacent graphite sheets of 0.335 nm to about 1.1 nm, preferably from about 0.335 nm to about 0.67 nm, and more preferably from about 0.335 to about 0.40 nm.
  • the catalysts used to prepare the carbon nanofibers of the present invention will depend on whether on wishes to produce “ribbon” structures or “platelet” structures. If “ribbon” structures are preferred the catalysts are comprised of iron or an iron: copper bulk bimetallic catalysts in powder form. If a “platelet” structure is preferred the catalyst will be an iron: copper bimetallic in powder form. It is well established that the ferromagnetic metals, iron, cobalt, and nickel, are active catalysts for the growth of carbon nanofibers during decomposition of certain hydrocarbons or carbon monoxide. Efforts are now being directed at modifying the catalytic behavior of these metals, with respect to nanofiber growth, by introducing other metals and non-metals into the system.
  • copper is an enigma, appearing to be relatively inert towards carbon deposition during the CO/H reaction.
  • Fe or the combination of Cu or Ni with Fe has such a dramatic effect on carbon nanofiber growth in the CO/H 2 system.
  • Iron copper catalysts are preferred for preparing the carbon nanostructures of the present invention.
  • the average powder particle size of the metal catalyst will range from about 0.5 nanometer to about 5 micrometer, preferably from about 2.5 nanometer to about 1 micrometer.
  • the ratio of the two metals can be any effective ratio that will produce substantially crystalline carbon nanofibers.
  • the ratio of iron to either copper or nickel will typically be from about 1:99 to about 99:1, preferably from about 5:95 to about 95:5, more preferably from about 3:7 to about 7:3; and most preferably from about 6:4 to about 7:3.
  • the bimetallic catalyst can be prepared by any suitable technique. One preferred technique is by co-precipitation of aqueous solutions containing soluble salts of the two metals.
  • Preferred salts include the nitrates, sulfates, and chlorides of iron and copper, particularly iron nitrate and copper nitrate.
  • the resulting precipitates are dried and calcined to convert the salts to the mixed metal oxides.
  • the calcined metal powders are then reduced at an effective temperature and for an effective time.
  • the catalyst powders used in the present invention are prepared by the co- precipitation of aqueous solutions containing appropriate amounts of iron, nickel and copper nitrates using ammonium bicarbonate.
  • the precipitates were dried overnight at about 110°C before being calcined in air at 400°C to convert the carbonates into mixed metal oxides.
  • the calcined powders were then reduced in hydrogen for 20 hours at 400°C. Following this treatment the reduced catalyst was cooled to room temperature in a helium environment before being passivated in a 2% oxygen/helium mixture for 1 hour at about room temperature (24°C).
  • composition of the gas phase was measured at regular intervals by taking samples of the inlet and outlet streams, which were then analyzed by gas chromatography using a 30m megabore (CS-Q) capillary column in a Varian 3400 GC unit. Carbon and hydrogen atom balances, in combination with the relative concentrations of the respective components, were applied to obtain the various product yields. In order to obtain reproducible carbon deposition data it was necessary to follow an identical protocol for each experiment.
  • the structural details of the carbon materials resulting from the interaction of the CO/H 2 mixtures with the various powdered bimetallic catalysts were examined in a JEOL 2000 EX II transmission electron microscope that was fitted with a high resolution pole piece capable of providing a lattice resolution of 0.18 nm.
  • Temperature programmed oxidation studies (TPO) of the various carbon materials were carried out in a Cahn 2000 microbalance in the presence of a CO 2 /Ar (1:1) mixture at a heating rate of 5°/min.
  • the degree of crystallization of a given type of carbon nanostructure was determined from a comparison of the oxidation profile of two standard materials, amorphous carbon and single crystal graphite when treated under the same conditions.
  • carbon nanostructures can be prepared by reacting a catalyst in a heating zone with the vapor of a suitable carbon-containing compound. While the art teaches a wide variety of carbon-containing compounds as being suitable, the inventors hereof have found that only a mixture of CO and H will yield carbon nanofibers with unexpected high crystallinities. That is, crystallinities greater than about 95%), preferably greater than 97% more preferably greater than 98%>, and most preferably substantially 100%.
  • nanofibers After the nanofibers are grown, it may be desirable to treat them with an aqueous solution of an inorganic acid, such as a mineral acid, to remove any excess catalyst particles.
  • suitable mineral acids include sulfuric acid, nitric acid, and hydrochloric acid. Preferred is hydrochloric acid.
  • the preferred intercalation compounds for use with the nanofibers of the present invention are alkali and alkaline-earth metals.
  • the limit to which the spacing of the graphite sheets will be increased for purposes of the present invention will be that point wherein the carbon nanofibers no longer can be characterized as graphitic. That is, the spacing can become so large that the carbon now has properties different than that of graphite. In most cases the electro-conductivity is enhanced. It is important for the practice of the present invention that the carbon nanofibers maintain the basal plane structure representative of graphite.
  • the carbon nanostructures of the present invention contain a substantial number of edge sites, also know as edge regions.
  • the edge regions of the nanofibers can be made either basic (introduction of NH + groups) or acidic (addition of COOFf groups) by use of appropriate methods.
  • oxygenated groups hydroxyl, peroxide, ether, keto or aldehyde
  • These groups in turn can react with organic compounds to those house unique structures for separatons.
  • Polar groups will promote the interaction of carbon edge atoms with other polar groups such as water.
  • the interaction of graphitic materials with aqueous solutions can be greatly enhanced due to the presence of acid, basic or neutral functionality.
  • polar groups in active carbon occurs in a random fashion, whereas in materials such as the graphite nanofibers of the present invention, such sites are always located at the edges of the graphene layers.
  • Addition of oxygenated groups can be achieved by selected oxidation treatments including treatment in peroxides, nitric acid, potassium permanganate, etc.
  • Functionality can also be incorporated by electrochemical oxidation, at for example 2.3 volts for various periods of time. The nature of the groups will be dependent upon the oxidation time and the voltage.
  • Polar sites can also be eliminated by reduction, out-gassing in vacuum at 1000°C or treatment in hydrazine at about 35°C. Following this procedure, the graphite nanofiber will become hydrophobic.
  • the most active catalysts were those that contained a larger fraction of iron than copper.
  • the overall degree of crystallinity of the carbon nanofibers produced from the interaction of selected Fe:Cu catalysts with a CO/H 2 (4: 1) mixture at 600°C for 2.0 hours was determined from temperature programmed oxidation of the nanofibers in CO 2 .
  • the characteristics of the controlled gasification of carbonaceous solids in CO 2 provides a sensitive method of determining the structural perfection of such materials.
  • Table V below indicates that the degree of crystallinity of carbon nanofibers generated from an Fe-Cu (7:3) catalyst is significantly higher than that of the same type of nanofibers grown under identical reaction conditions on a pure iron catalyst.
  • a carbon nanofiber having graphite sheets at an angle to the longitudinal axis of the nanofiber is referred to as a "herringbone structure”.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Thermal Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Catalysts (AREA)
  • Inorganic Fibers (AREA)

Abstract

L'invention concerne un procédé de production de nanofibres de carbone graphitique sensiblement cristallin constituées de feuilles de graphite. Les feuilles de graphite sont sensiblement parallèles ou sensiblement perpendiculaires à l'axe longitudinal de la nanofibre de carbone. Lorsque les feuilles de graphite doivent être sensiblement parallèles, ces nanofibres de carbones sont produites par mise en contact de catalyseur en masse à base de fer ou bimétallique à base de fer:cuivre, ou de fer:nickel, avec un mélange de monoxyde carbone et d'hydrogène à des températures comprises entre 670 °C environ et 725 °C environ pendant une durée effective. Lorsque les feuillets de graphite doivent être sensiblement perpendiculaires, les nanofibres sont produites par l'utilisation d'un catalyseur en masse bimétallique fer:cuivre à des températures comprises entre 550 °C environ et 670 °C environ.
PCT/US2001/028199 2000-09-08 2001-09-07 Nanofibres de graphite cristallin et procede de production correspondant WO2002020401A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CA002420004A CA2420004A1 (fr) 2000-09-08 2001-09-07 Nanofibres de graphite cristallin et procede de production correspondant
EP01968718A EP1349808A4 (fr) 2000-09-08 2001-09-07 Nanofibres de graphite cristallin et procede de production correspondant

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US09/659,441 US6537515B1 (en) 2000-09-08 2000-09-08 Crystalline graphite nanofibers and a process for producing same
US09/659,441 2000-09-08
US09/902,113 2001-07-10
US09/902,113 US20020054849A1 (en) 2000-09-08 2001-07-10 Crystalline graphite nanofibers and a process for producing same

Publications (1)

Publication Number Publication Date
WO2002020401A1 true WO2002020401A1 (fr) 2002-03-14

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US (2) US20020054849A1 (fr)
EP (1) EP1349808A4 (fr)
CA (1) CA2420004A1 (fr)
WO (1) WO2002020401A1 (fr)

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EP1349808A1 (fr) 2003-10-08
EP1349808A4 (fr) 2006-02-01
US20040071625A1 (en) 2004-04-15
US20020054849A1 (en) 2002-05-09

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