WO2004037715A2 - Procede basse temperature de preparation de metallofullerenes endohedriques de nitrure trimetallique - Google Patents

Procede basse temperature de preparation de metallofullerenes endohedriques de nitrure trimetallique Download PDF

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Publication number
WO2004037715A2
WO2004037715A2 PCT/US2003/021692 US0321692W WO2004037715A2 WO 2004037715 A2 WO2004037715 A2 WO 2004037715A2 US 0321692 W US0321692 W US 0321692W WO 2004037715 A2 WO2004037715 A2 WO 2004037715A2
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WIPO (PCT)
Prior art keywords
metal
reactor
trimetallic nitride
carbon
nitrogen containing
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Application number
PCT/US2003/021692
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English (en)
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WO2004037715A3 (fr
Inventor
Harry C. Dorn
Clayton Mckee
Jim Duchamp
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Virginia Tech Intellectual Properties, Inc.
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Priority to AU2003301557A priority Critical patent/AU2003301557A1/en
Publication of WO2004037715A2 publication Critical patent/WO2004037715A2/fr
Publication of WO2004037715A3 publication Critical patent/WO2004037715A3/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
    • 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
    • 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
    • C01B32/154—Preparation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • 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
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds

Definitions

  • the invention is directed to the preparation of endohedral metallofullerenes and, more particularly to a low temperature method for forming trimetallic nitride endohedral metallofullerenes.
  • Fullerenes are a family of closed-caged molecules made up of carbon atoms.
  • the closed-caged molecules consist of a series of five and six member carbon rings.
  • the fullerene molecules can contain 500 or more carbon atoms.
  • the most common fullerene is the spherical C 6 o molecule.
  • Fullerenes are typically produced by an arc discharge method using a carbon rod as one or both of the electrodes in a Kratschiner-Huffman generator.
  • the generator has a reaction chamber and two electrodes.
  • the reaction chamber is evacuated and an inert gas is introduced in the reaction chamber at a controlled pressure.
  • a potential is applied between the electrodes in the chamber to produce an arc discharge.
  • the arc discharge forms a carbon plasma in which fullerenes of various sizes are produced.
  • fullerenes Many derivatives of fullerenes have been prepared including encapsulating metals inside the fullerene cage.
  • Metal encapsulated fullerenes are typically prepared by packing a cored graphite rod with the metal oxide of the metal to be encapsulated in the fullerene cage. The packed graphite rod is placed in the generator and arc discharged to produce fullerene products.
  • the fo ⁇ nation of metal encapsulated fullerenes is a complicated process and typically yields only very small amounts of the metal fullerenes.
  • the metals A and X may be an element selected from the group consisting of a rare earth element and a group IIIB element and may be the same or different.
  • a and X may be selected from the group consisting of Scandium, Yttrium, Lanthanum, Gadolinium, Holmium, Erbium, Thulium, and Ytterbium, where A and X may be the same or different.
  • TNT trimetallic nitride template
  • Trimetallic nitride endohedral metallofullerenes have significant interest because of the ability to encapsulate a variety of different types of metals for a variety of applications such as superconductor materials, catalysts, nonlinear optical materials, molecular carriers for drugs, or carriers useful in missile therapy for cancer and as a radionuclide tracer. Due to the many possible applications for the endohedral metallofullerenes, additional methods for forming endohedral metallofullerenes are currently being investigated.
  • the invention is directed to a low temperature method for forming endohedral metallofullerenes that does not require the use of a &atschmer-Huffman generator, which typically have arc temperatures of 3000 K to 4000 K.
  • the invention includes a method for forming trimetallic nitride endohedral metallofullerenes comprising the steps of charging a reactor with carbon, a nitrogen containing compound, and a metal; sealing the reactor under vacuum to form a sealed reactor; and heating the sealed reactor at a temperature and for a time effective to form a trimetallic nitride endohedral metallofullerene.
  • the invention includes a method for forming a trimetallic nitride endohedral metallofullerene, comprising the steps of charging a reactor with a first metal, a second metal, carbon, and a nitrogen containing compound; sealing the reactor under vacuum; and heating the reactor to a temperature and for a time effective to form a trimetallic nitride endohedral metallofullerene.
  • the invention is directed to a low temperature method for forming endohedral metallofullerenes, and more particularly to forming trimetallic nitride endohedral metallofullerenes.
  • endohedral refers to the encapsulation of atoms inside the fullerene cage network. Accepted symbols for elements and subscripts to denote numbers of elements are used herein. Further, all elements to the right of an @ symbol are part of the fullerene cage network, while all elements listed to the left are contained within the fullerene cage network.
  • Sc 3 N@C_o indicates that the Sc 3 N trimetallic nitride is situated inside the framework of a C 80 fullerene cage.
  • the metal atoms are may be trivalent and have an ionic radius below about 0.095 nm.
  • the metal atoms may have an ionic radius below about 0.090 nm for the A 3 N endohedral species.
  • the larger atomic radius of 0.095 nm for A can be accommodated.
  • the ionic radius for the metal may increase.
  • a and X may be a rare earth element, a group IIIB element, or the like.
  • a or X may be Scandium, Yttrium, Lanthanum, Gadolinium, Holmium, Erbium, Thulium, and Ytterbium.
  • the method for making a trimetallic nitride endohedral metallofullerene includes charging a reactor with carbon, a metal, and a nitrogen containing compound.
  • the reactor is sealed under vacuum and heated to a temperature and for a time effective to form a trimetallic nitride endohedral metallofullerene having the general formula A 3 N@C m , where A is the metal and m ranges from about 60 to about 200.
  • the particular form of carbon used to charge the reactor is not particularly limited so long as the carbon will form a fullerene cage structure under the reaction conditions of the invention.
  • the carbon may include carbon or hydrocarbon precursors with bowl-like sp 2 hybridized carbon atoms that may be used as a starting template for fullerene cage formation for the endohedral metallofullerene.
  • the carbon charged in the reactor may include an empty-caged fullerenes, including but not limited to Ceo-
  • the metal that is used to charge the reactor may be a trivalent metal and may include a rare earth metal or a group IIIB metal.
  • the metal may include, but is not limited to Scandium, Yttrium, Lanthanum, Gadolinium, Holmium, Erbium, Thulium, and Ytterbium.
  • the metal source for supplying the metal may include, for example, the corresponding metal oxide, such as, Sc 2 O 3 , Er 2 O 3 , Ho 2 O 3 , Y 2 O 3 , La 2 O 3 , Gd 2 O 3 , Tm 2 O 3 , or Yb 2 O 3 .
  • the nitrogen containing compound provides the source of nitrogen for the trimetallic nitride complex that resides in the cage of the trimetallic nitride endohedral metallofullerene.
  • the nitrogen containing compound is not particularly limited provided that it reacts with the metal source to form the trimetallic nitride complex for the
  • Nitrogen containing compounds may by solids or gases so long as they react with the metal source to form the desired trimetallic nitride complex.
  • the reactor should be charged with amounts of carbon, the metal source, and ' nitrogen containing compound effective to form the desired trimetallic nitride endohedral metallofullerene when the reactor is heated to a temperature ranging from about 800 K to about 1800 K.
  • the amounts of carbon, the metal source, and the nitrogen containing compound will vary depending on the carbon being used, the metal source being used, the nitrogen containing compound being used, and the reaction conditions such as temperature, time, and pressure.
  • 130 mgs of C 6 o, 30 mg SC 2 O 3 , and 30 mg of iron nitrate were effective to form Sc 3 N@C 84 after heating at l250 K for 24 hrs.
  • the reactor is then heated at a temperature and for a time effective to form trimetallic nitride endohedral metallofullerene compounds.
  • the reactor may be heated to a temperature ranging from about 800 K to about 1800 K. In one embodiment, the reactor is heated to about 1250 K.
  • the time required to form the trimetallic nitride endohedral metallofullerene compounds may vary depending on the reactants used to charge the reactor, the temperature used to heat the reactor, and other conditions known to those skilled in the art.
  • a reaction time of about 24 hours is sufficient to form a trimetallic nitride endohedral metallofullerene.
  • the reactor may be a quartz tube, but can be made from any suitable material that can withstand the above described reaction
  • the reactor should be able to hold a vacuum during heating and must be able to withstand the reaction temperatures. Further, the material of the reactor should not react with the carbon, metal or metals, or the nitrogen containing compound.
  • a second metal may be added to the reactor.
  • the reactor is charged with carbon, a first metal, a second metal, and a nitrogen containing compound.
  • the reactor is sealed under vacuum and heated to the desired temperature for a time effective to form the trimetallic nitride endohedral metallofullerene.
  • the carbon and nitrogen containing material should have the same characteristics as those described above.
  • the first metal and second metal may be a trivalent metal and may include a rare earth metal or a group IIIB metal.
  • the first metal and second metal may include, but are not limited to Scandium, Yttrium, Lanthanum, Gadolinium, Holmium, Erbium, Thulium, and Ytterbium.
  • first metal and second metal may be selected from the same group of metals, in some embodiments, the first metal and the second metals are different to form a trimetallic nitride endogedral metallofullerene having the general formula A3_ n X n N@C m , where A is the first metal, X is the second metal, n ranges from 1 to 3, and m ranges from about 60 to about 200.
  • the first metal and the second metal are added to the reactor in the form of a metal source, which may include, but is not limited to, the respective metal oxide.
  • Representative metal oxides may include, but are not limited to, Sc 2 O 3 , Er 2 O 3 , Ho 2 O 3 , Y 2 O 3 , La 2 O 3 , Gd 2 O 3 , Tm 2 O 3 , or Yb 2 O 3 .
  • the ratio of first metal oxide to second metal oxide may range from about 1 : 1 to about 3:1 depending on the ratio of metals desired in the endohedral metallofullerene.
  • the reactor should be charged with amounts of carbon, the first metal source, the second metal source, and nitrogen containing compound effective to form the desired
  • the reactor may be opened and the resulting soot containing the reaction products may be removed.
  • Isolation of the trimetallic nitride endohedral metallofullerenes consists of using carbon disulfide or toluene to extract the soluble fullerenes from the soot. All members of the trimetallic nitride endohedral metallofullerenes, Er 3 , n Sc n N@C 8 o, H ⁇ 3 - n Sc n N@C 80 , Y3- n Sc n N@C 8 o, Gd 3 .
  • n Sc n N@C 8 o and La 3 - n Sc n N@C 8 o where n 0-3, are extractable in carbon disulfide except Yb3.
  • n Sc n N@C 8 o and Tm 3 _ n Sc n N@C 8 o (n 0-3). While the separation method is described for A 3 _ n X n N@C 8 o it is also applicable to other trimetallic nitride endohedral metallofullerenes such as A 3 _ n X n N@C 68 and A 3 _ n X n N@C 78 . The separation methods are the same as those described in U.S. Patent No. 6,303,760, herein incorporated by reference in its entirety.
  • trimetallic nitride endohedral metallofullerenes having the general formula A 3 _ n X n N@C m are produced using the above described low temperature method.
  • Using the method of the invention reduces the temperature at which trimetallic endohedral metallofullerenes are produced when compared to the high arc temperature of the &atschmer-Huffman generator.

Abstract

L'invention concerne un procédé de formation de métallofullerènes endohédriques de nitrure trimétallique de formule générale A3-nXnN@Cm, dans laquelle A représente un premier métal, X est éventuellement un second métal, n représente un entier entre 0 et 3 et m représente un entier compris entre 60 et 200 environ. Le procédé consiste à chauffer un mélange de carbone, de premier métal, éventuellement de second métal, et d'un composé azoté dans un réacteur scellé sous vide à une température et pendant une durée suffisantes pour former des métallofullerènes endohédriques de nitrure trimétallique.
PCT/US2003/021692 2002-07-12 2003-07-11 Procede basse temperature de preparation de metallofullerenes endohedriques de nitrure trimetallique WO2004037715A2 (fr)

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AU2003301557A AU2003301557A1 (en) 2002-07-12 2003-07-11 Low temperature method for preparing trimetallic nitride endohedral metallofullerenes

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US60/395,327 2002-07-12

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113023690A (zh) * 2019-12-25 2021-06-25 中国科学院化学研究所 金属氮化物内嵌富勒烯及其制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6303760B1 (en) * 1999-08-12 2001-10-16 Virginia Tech Intellectual Properties, Inc. Endohedral metallofullerenes and method for making the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6303760B1 (en) * 1999-08-12 2001-10-16 Virginia Tech Intellectual Properties, Inc. Endohedral metallofullerenes and method for making the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113023690A (zh) * 2019-12-25 2021-06-25 中国科学院化学研究所 金属氮化物内嵌富勒烯及其制备方法
CN113023690B (zh) * 2019-12-25 2023-01-24 中国科学院化学研究所 金属氮化物内嵌富勒烯及其制备方法

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AU2003301557A1 (en) 2004-05-13
AU2003301557A8 (en) 2004-05-13

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