WO2008097333A2 - Procédé et dispositif de fabrication à basse température de carbone graphitique, de graphène et de nanotubes de carbone - Google Patents

Procédé et dispositif de fabrication à basse température de carbone graphitique, de graphène et de nanotubes de carbone Download PDF

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Publication number
WO2008097333A2
WO2008097333A2 PCT/US2007/072858 US2007072858W WO2008097333A2 WO 2008097333 A2 WO2008097333 A2 WO 2008097333A2 US 2007072858 W US2007072858 W US 2007072858W WO 2008097333 A2 WO2008097333 A2 WO 2008097333A2
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WO
WIPO (PCT)
Prior art keywords
solution
graphitic carbon
heating
solid
solvent
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Application number
PCT/US2007/072858
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English (en)
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WO2008097333A3 (fr
Inventor
Louis Eugene Brus
Michael Louis Steigerwald
Erich Walter
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The Trustees Of Columbia University In The City Of New York
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Application filed by The Trustees Of Columbia University In The City Of New York filed Critical The Trustees Of Columbia University In The City Of New York
Publication of WO2008097333A2 publication Critical patent/WO2008097333A2/fr
Publication of WO2008097333A3 publication Critical patent/WO2008097333A3/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
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C01B32/17—Purification

Definitions

  • the disclosed subject matter relates to techniques for the preparation of graphitic carbon, including carbon nanotubes.
  • Such extreme conditions may be dictated by the need to fragment stable carbon sources and/or by the difficulty intrinsic to ordering the initially-prepared carbon network.
  • a lower-temperature and controllable process for the preparation of graphitic carbon would facilitate progress in these research areas by enabling the rational synthesis of appropriate carbon specimens.
  • Plasma-enhanced chemical vapor deposition has been proposed as an alternative technique wherein the carbon source material is subjected to lower reaction chamber temperatures, e.g., 400° C. See, e.g., U.S. patent application publication no. US2005/0233263 Al to Park et al. However, as discussed in U.S. Patent No. 7,052,667 to Loutfy et al., the plasma itself is at several thousand degrees C. A need therefore remains for a controllable low temperature technique for the fabrication of graphitic carbon.
  • the disclosed subject matter provides methods for preparing graphitic carbon, includes combining at least partially reduced soluble iron, a cyclic, nonconjugated polyolefin, and a solvent to form a solution, heating the solution until reflux, adding an oxidizing agent to the solution to form a second solution, and heating the second solution to form a solid, thereby forming graphitic carbon.
  • the graphitic carbon prepared from this reaction can include carbon nanotubes and/or sheets of graphitic carbon.
  • the solutions can be agitated while being heated using e.g., a magnetic spinbar or a mechanical shaker or other means for agitating the solution.
  • the cyclic, nonconjugated polyolefin can be cyclooctatetraene (COT).
  • COT is in the form of bis(cyclooctatetraene)iron.
  • the solvent can be any suitable solvent, for example, toluene, benzene, heptadecane, diphenyl ether, and/or hexane.
  • the oxidizing agent can be, for example, diphenylsulfoxide, diphenylselenoxide, diphenyltelluroxide, trimethylamine-N-oxide, pyridine-N-oxide, and/or dimethylsulfoxide (DMSO).
  • DMSO dimethylsulfoxide
  • the solution optionally further includes dimethoxyethane (DME).
  • the second solution is heated at a low temperature, for example a temperature below 500°C. In one embodiment, the second solution is heated at a temperature of between about 100 0 C and about 13O 0 C, e.g., about 115°C. The second solution is heated for a time period to allow formation of a solid.
  • the second solution is heated for between about 12 hours and about 120 hours.
  • the method for preparing graphitic carbon further includes washing the solid with concentrated mineral acid, e.g., hydrochloric acid.
  • the reaction can take place in an inert gas atmosphere, e.g., nitrogen, argon, or helium.
  • an inert gas atmosphere e.g., nitrogen, argon, or helium.
  • the reaction takes place in a vessel such as a Schlenk tube.
  • the disclosed subject matter also provides methods for preparing graphitic carbon by combining bis(cyclooctatetraene)iron (Fe(COT) 2 ), dimethoxyethane (DME), and a solvent to form a solution, heating the solution until reflux, adding dimethylsulfoxide (DMSO) to the solution to form a second solution, and heating the second solution to form a solid, thereby forming graphitic carbon.
  • DMSO dimethylsulfoxide
  • the disclosed subject matter provides methods for preparing graphitic carbon comprising combining COT with dimethylsulfoxide
  • FIG. 1 is a block diagram of an apparatus in accordance with the disclosed subject matter.
  • FIG. 2 is an SEM image of tubular nanocrystals formed in accordance with the disclosed subject matter.
  • the SEM image depicts Fe(COT)2 + DME + DMSO powder sputter coated with Pd/ Au.
  • FIGs. 3(a)-(d) are TEM images showing sheets and tubes before and after an acid wash.
  • FIG 3(e) is a selective area electron diffraction pattern corresponding to Figs. 3(a)-(d).
  • FIGs. 4(a), (b) and (d) are TEM images showing tubes.
  • FIG 4(c) is a selective area electron diffraction pattern corresponding to Figs. 4(a), (b) and (d).
  • FIG. 5 is a graph showing a Raman shift.
  • the same reference numerals and characters, unless otherwise stated, are used to denote like features, elements, components or portions of the illustrated embodiments.
  • the disclosed subject matter will now be described in detail with reference to the Figs., it is done so in connection with the illustrative embodiments.
  • the disclosed subject matter provides a method and apparatus for the preparation of graphitic carbon, sheets as well as tubes, from readily available solvent reagents at temperatures under about 500° C.
  • a suitable vessel e.g., a vacuum vessel such as a Schlenk tube 110, including a stopper 120 and a socket joint 130 at its sidearm, can be utilized.
  • the socket joint 130 is suitable for connection to a vacuum manifold for introducing overpressure via an inert gas, such as argon, nitrogen, or helium at atmospheric or other pressures.
  • an inert gas such as argon, nitrogen, or helium at atmospheric or other pressures.
  • a magnetic spinbar 140 and solution containing the reagents needed to form graphitic carbon 150 are introduced into the Schlenk tube 110.
  • the Schlenk tube 110 is placed in a suitable oil bath 160 to provide necessary heat to react the reagents within the solution 150.
  • the solution 150 is a mixture of at least partially reduced soluble iron, a cyclic, nonconjugated polyolefin, and a solvent.
  • the solution is heated until reflux, and an oxidizing agent is added to the solution to form a second solution.
  • Any oxidizing agent may be used, for example, dimethylsulfoxide (DMSO).
  • Suitable oxidizing agents are diphenylsulfoxide, diphenylselenoxide, diphenyltelluroxide, trimethylamine-N-oxide, and pyridine-N-oxide.
  • suitable sources of iron and oxygen such as independently prepared iron oxide nanoparticles, may be utilized.
  • the solution optionally further comprises dimethoxyethane (DME) or another composition useful in increasing solubility.
  • DME dimethoxyethane
  • the term "partially reduced soluble iron” includes a chemical compound that is soluble and/or dispersible in an organic solvent and that contains iron in an oxidation state less than 3.
  • cyclic, nonconjugated polyolefin includes a hydrocarbon having the general chemical formula C n H n and containing a ring of alternating C-C single and C-C double bonds. Examples include cyclobutadiene and cyclododecahexaene in addition to cyclooctatetraene.
  • the cyclic, nonconjugated polyolefin includes cyclooctatetraene (COT).
  • the COT is in the form of bis(cyclooctatetraene)iron.
  • simple acetylenes such as C 2 H 2 may be utilized.
  • any suitable solvent may be utilized.
  • This solvent must be capable of dissolving and/or dispersing the iron-containing compound, and it must be capable of dissolving and/or dispersing the hydrocarbon compound.
  • the solvent can be toluene, benzene, heptadecane, diphenyl ether, and/or hexane.
  • the solution is a mixture of bis (cyclooctatetraene)iron
  • Fe(COT) 2 Fe(COT) 2
  • DME DME
  • toluene 0.38 mmol of Fe(COT) 2 , 1.52 mmol of DME and 40 ml of toluene may form the solution 150.
  • the solution is brought to reflux and an oxidizing agent, e.g., dimethylsulfoxide ("DMSO"), is added.
  • DMSO dimethylsulfoxide
  • 1.52 mmol of DMSO is added.
  • the solution is a mixture of bis(cyclooctatetraene)iron (Fe(COT) 2 ), dimethoxyethane (DME), and a solvent.
  • An oxidizing agent, e.g., DMSO is added at reflux to form a second solution.
  • COT with an oxidizing agent e.g., dimethylsulfoxide (DMSO) is mixed with a solvent to form a solution.
  • DMSO dimethylsulfoxide
  • Iron pentacarbonyl (Fe(C0)5 is added at reflux to form a second solution.
  • the second solution is maintained at an elevated, but low temperature, e.g., a temperature below 500°C, for example approximately 100°C, 125°C, 15O 0 C, 175°C, 200°C, 225°C, 250°C, 275°C, 300 0 C, 325°C, 350 0 C, 375°C, 400 0 C, 425°C, 450 0 C, 475°C or 500° C, and for a sufficient period of time, i.e., approximately 6, 9, 12, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, or 120 hours, or longer to permit the reactants to form graphitic carbon.
  • the temperature is elevated, it is relatively cool compared to the temperatures required for CVD, PECVD and other prior art techniques. In a preferred arrangement, the temperature is kept at approximately 115° C, and the solution
  • the solution 150 transforms into a solution over a solid.
  • the solid comprises graphitic carbon, e.g., carbon nanotubes and sheets.
  • the solution 150 is then cooled to room temperature, and any remaining supernatant solution is removed.
  • the deposited solid material in one embodiment, is collected and may be rinsed with a solvent, e.g., pentane (3 x 10 ml) and dried, e.g., in a vacuum, resulting in a brown-black powder containing millimeter- sized fragments of a reflective black solid.
  • a solvent e.g., pentane (3 x 10 ml
  • a SEM image of the deposited solid material will be described. As illustrated, the material includes large amounts of long, tubular structures. Those structures are made primarily of carbon, with smaller amounts of iron and oxygen.
  • Figs. 3(a)-(e) the deposited solid material will now be described with reference to TEM images. As shown in Figs. 3(a) and (b), micron- scale tubes and sheets in addition to nanoparticles of FeOx are formed.
  • SAED Selective Area Electron Diffraction
  • Figs. 4(a)-(e) show representative images of two samples produced in the same five day long reaction, as-synthesized and acid-washed. The grids are dominated by areas of crystalline graphite and MWCNTs.
  • Fig. 4 (d) depicts a HRTEM image from an acid-washed sample, and it is not crystalline.
  • Fig. 5 the Raman spectrum of the black solid shown in Figs. 2-4 is presented. As show, both the D (-1350 cm “1 ) and G (-1600 cm “1 ) modes of graphite are present. The peaks at 130 cm “1 and 172 cm “1 may be attributed to radial breathing modes of CNTs. The Raman spectra also shows that treating the product with acid appears to damage the graphitic carbon, as acid-treated samples display only weak, broad peaks at 1350 cm “1 and around 1590 cm “1 . Nanoparticles have drawn interest for use as potential catalysts due to their high surface to volume ratio and possible chemical selectivity (crystal facet/chirality/molecular recognition).
  • the catalytic activity of metals is strongly size dependant. Synthesizing graphite and carbon nanotubes at lower temperatures and in solution, in accordance with the disclosed subject matter, may lead to more control of the synthesis with regard to regrowth, functionalization, size control, preferential growth of carbon tubes vs. sheets, cleanliness, solublization and phase.

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

Abstract

La présente invention concerne des techniques de fabrication contrôlable à basse température de carbone graphitique. La présente invention concerne en outre un procédé chimique utilisant des hydrocarbures disponibles dans le commerce pour la préparation de carbone graphitique, y compris des nanotubes et des feuilles de carbone.
PCT/US2007/072858 2006-07-06 2007-07-05 Procédé et dispositif de fabrication à basse température de carbone graphitique, de graphène et de nanotubes de carbone WO2008097333A2 (fr)

Applications Claiming Priority (2)

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US81884006P 2006-07-06 2006-07-06
US60/818,840 2006-07-06

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WO2008097333A3 WO2008097333A3 (fr) 2008-11-27

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013093358A1 (fr) 2011-12-22 2013-06-27 Arkema France Procede de production d'un assemblage de nanotubes de carbone et de graphene
US8515557B2 (en) 2007-11-19 2013-08-20 Cochlear Limited Electrode array for a cochlear implant
US9589580B2 (en) 2011-03-14 2017-03-07 Cochlear Limited Sound processing based on a confidence measure

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3773632A (en) * 1970-02-17 1973-11-20 Studiengesellschaft Kohle Mbh Electrochemical production of transition metal organometallic complexes
US4782034A (en) * 1987-06-04 1988-11-01 American Telephone And Telegraph Company, At&T Bell Laboratories Semi-insulating group III-V based compositions doped using bis arene titanium sources
US20030220518A1 (en) * 2001-10-01 2003-11-27 Bolskar Robert D. Derivatization and solubilization of fullerenes for use in therapeutic and diagnostic applications
US6841139B2 (en) * 1998-09-18 2005-01-11 William Marsh Rice University Methods of chemically derivatizing single-wall carbon nanotubes
US7008604B2 (en) * 1997-03-07 2006-03-07 William Marsh Rice University Method for cutting nanotubes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3773632A (en) * 1970-02-17 1973-11-20 Studiengesellschaft Kohle Mbh Electrochemical production of transition metal organometallic complexes
US4782034A (en) * 1987-06-04 1988-11-01 American Telephone And Telegraph Company, At&T Bell Laboratories Semi-insulating group III-V based compositions doped using bis arene titanium sources
US7008604B2 (en) * 1997-03-07 2006-03-07 William Marsh Rice University Method for cutting nanotubes
US6841139B2 (en) * 1998-09-18 2005-01-11 William Marsh Rice University Methods of chemically derivatizing single-wall carbon nanotubes
US20030220518A1 (en) * 2001-10-01 2003-11-27 Bolskar Robert D. Derivatization and solubilization of fullerenes for use in therapeutic and diagnostic applications

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8515557B2 (en) 2007-11-19 2013-08-20 Cochlear Limited Electrode array for a cochlear implant
US9589580B2 (en) 2011-03-14 2017-03-07 Cochlear Limited Sound processing based on a confidence measure
US10249324B2 (en) 2011-03-14 2019-04-02 Cochlear Limited Sound processing based on a confidence measure
WO2013093358A1 (fr) 2011-12-22 2013-06-27 Arkema France Procede de production d'un assemblage de nanotubes de carbone et de graphene

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