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WO1993011067A1 - Nouveaux sels de fullerenes - Google Patents

Nouveaux sels de fullerenes Download PDF

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Publication number
WO1993011067A1
WO1993011067A1 PCT/US1992/010120 US9210120W WO9311067A1 WO 1993011067 A1 WO1993011067 A1 WO 1993011067A1 US 9210120 W US9210120 W US 9210120W WO 9311067 A1 WO9311067 A1 WO 9311067A1
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WO
WIPO (PCT)
Prior art keywords
fullerene
group
anion
composition
potential
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Application number
PCT/US1992/010120
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English (en)
Inventor
Sergiu Mircea Gorun
Mark Alan Greaney
Donald Martin Cox
Russell Robert Chianelli
Edward Ira Stiefel
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Exxon Research And Engineering 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 Exxon Research And Engineering Company filed Critical Exxon Research And Engineering Company
Priority to EP93900639A priority Critical patent/EP0614444A4/fr
Priority to JP5510208A priority patent/JPH07501782A/ja
Publication of WO1993011067A1 publication Critical patent/WO1993011067A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • C01B32/156—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/14—Alkali metal compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to novel salts of fullerenes, also known as fulleride salts, their preparation and use.
  • Diamond and graphite are two well known allotropic forms of carbon. Another form, the fullerenes, have been prepared by graphite volatilization (See W. Kratschmer et al , Nature, 347, p. 354 (1990)). Potassium and other metal complexes of fullerenes have been observed in the gas phase by mass spectrometry (See D. M. Cox et al , J. Chem. Phvs. 88(3), 1588 (1988)).
  • Fullerenes are hollow molecules composed only of carbon atoms and constitute a new allotropic form of carbon. Typically, fullerenes each have carbon atoms arranged as 12 pentagons, but differing numbers of hexagons having the formula C2n where n is equal to or greater than 16 (hereinafter “fullerenes”). The pentagons are required in order to allow the curvature and eventual closure of the closed surface upon itself.
  • the most abundant species of fullerenes identified to date is the C60 molecule or Buck insterfullerene (here ⁇ inafter "C6 ⁇ "). C60 consists of 12 pentagons and 20 hexagons. However, other species, including C70 have also been identified.
  • Preferred monovalent cations include ammonium cations, alkyl ammonium cations such as quater ⁇ nary ammonium cations, alkali metal cations, phosphonium and arsoniu cations, especially organophosphonium and organoarsonium ions, partic ⁇ ularly phenylphosphonium and phenylarsonium cations.
  • the preferred fullerene used in the practice of the present invention is C60-
  • the fulleride salt compounds of the present invention are prepared by passing an electric current through (electrolyzing) a non-aqueous solution of fullerenes in the presence of a soluble salt containing a cation, A, of the A n C ⁇ compound to be formed. The electric potential is applied for a time sufficient to generate fullerene anions in the solution.
  • the fulleride salt compounds are prepared in the solid state. The compounds of the present invention exhibit reversible electrochemical reduction; and, consequently, are particularly useful as electrode components in electrochemical cells such as secondary batteries.
  • the fullerene anions, Ceo'- ⁇ and C70 ⁇ y, wherein y is a charge of from 1 to 3, specifically 1, 2, and 3 in the compound of the present invention contain unpaired electrons and thus have paramag ⁇ netic properties.
  • C6o ⁇ l and C ⁇ o---- these properties are confirmed by electron spin resonance spectroscopy ("ESR") for the tetralkyl ammonium fulleride salt containing the C60 ⁇ * monoanion.
  • ESR electron spin resonance spectroscopy
  • the magnitude of the magnetic susceptibility of the compound of the present invention varies with the temperature accord ⁇ ing to the Curie-Weiss law, which is known to one having ordinary skill in the art. Since a one-to-one magnetic susceptibility tempera ⁇ ture correspondence exists, these compounds may be used as magnetic thermometers.
  • fulleride salts containing C60" 1 monoanions may be used as semiconductors (See P. M. Allemand et al., J. Am. Chem. Soc., 113,2780 (1991)) while those containing C60" 3 and alkali-metals may be used as superconductors (See A. F. Hebard et al., Nature 350,600 (1991)).
  • Alkali salts of C60 also can serve as starting materials for the preparation of other materials.
  • the reaction of the lithium salt of Ceo, for example, with alkyl halides yield alkyl derivatives of fullerenes (See J. W. Bausch et al., J. Am. Che . Soc 113,3205 (1991)) that may be useful as polymer blends, composites and building blocks.
  • the A n C x fulleride salts are stable in the absence of air and other reactive molecules. Their free radical character may make them suitable as spin labels.
  • Spin labels are usually organic molecules that contain an unpaired electron (for example, a nitroxyl radical) and are used to render diamagnetic molecules to which they are attached susceptible to analysis by magnetic spin resonance techniques.
  • the A n C x spin labels mixed, for example with polymers, may allow valuable information concerning polymer dynamics and struc ⁇ tures to be obtained.
  • the present invention encompasses novel compositions of matter having the formula A n C x , wherein C x is a fullerene anion, wherein C x is preferably selected from the group consisting of C ⁇ o and C70, wherein A is a monovalent cation and wherein n is an integer from 1 to 3 inclusive, specifically 1, 2, and 3.
  • the cation, A may be selected from a wide range of cations.
  • the fullerene anion is further selected from the group consisting of monovalent, divalent and tri- valent anions. Its valence, however, depends on the formula of the monovalent cation, A n .
  • C x will be a monovalent anion; where A n has the formula (A+l)2, C x will be a divalent anion; for (A+l)3, C x will be a trivalent anion.
  • Particularly preferred cations for A include ammonium and alkyl ammonium cations, organophosphoniu or organoarsonium cations, especially tetraorganophosphoniu and tetra- organoarsonium ions, such as tetraphenylphosphonium and tetraphenyl- arsonium cations, alkali metal cations, and the like.
  • the alkali metal cations Li, Na and K are especially preferred.
  • the preferred fullerene used in the practice of the present invention is C60-
  • the starting materials for the practice of the present invention can be obtained from commercial sources.
  • the fullerenes may be prepared by graphite volatilization (see W. Kratschmer, et al, Nature. 347, p. 354 (1990)).
  • Non-aqueous as used herein means solvent systems wherein water, if present, is electrochemically and chemically inert.
  • toluene, dichloromethane in the case where the cation, A, is organic and a high polarity solvent such as dimethyl sulfoxide when the cation A is inorganic.
  • a high polarity solvent such as dimethyl sulfoxide when the cation A is inorganic.
  • Single, binary or multicomponent mixtures of tetrahy- drofuran, ethylene chloride, toluene, xylenes, dimethyl sulfoxide, dichloromethane, benzene are particularly suitable for dissolving the fullerenes.
  • the salt containing the cation, A, of desired compound, A n C x must have some solubility in the organic solvent system used.
  • salts containing organo groups such as, but not restricted to, R4NCI, R4ASU, R4PCI, R4NPF6, and R4NBF4 are particularly suitable.
  • R is selected from the group consisting of hydrogen and an organic moiety.
  • the organic moiety should be chosen in order to render the salt soluble in the solvent system. It is within the skill of one of ordinary skill in the art to make a selection of the appropriate solvent system.
  • R may, for example, be selected from alkyl groups having from 1 to 16 carbon atoms and phenyl groups.
  • Other useful salts include alkali metal salts having anions containing sufficient organic moieties to render the salt soluble in the solvent system.
  • Representative examples include NaBPh4, KBPh4 where ("Ph” as used herein means phenyl or substituted phenyl group).
  • the solvent system is more polar.
  • Inorganic salts such as NaBF4, KC1 and KBr should be used with mixtures of tetrahydrofuran, dimethyl sulfoxide, dimethyl formamide, toluene and the like.
  • the relative ratio of components of the solvent mixtures should be such as to insure some degree of solubility of both starting materials; i.e., fullerenes (which are soluble in relatively non-polar solvents) and inorganic salts (more soluble in polar sol ⁇ vents like dimethyl sulfoxide).
  • a commercially available PAR (Princeton Applied Research) System equipped with Pt wire auxiliary electrode, standard calomel reference electrode (SCE) and a Pt gauze working electrode may be used to reduce, for example, up to gram quantities of the particular fullerene. Other commercial units may be used to prepare larger quantities of fulleride salts.
  • a potentiostat regulates the potential necessary to produce the desired reduction state (salt of anion) of the fullerene in the particular solvent system.
  • the molar ratio of salt to fullerene used in the solvent system will be generally greater than 3:1 and, preferably, will be in the range of about 10 to 20.
  • the potential may be applied using any known source of direct current after immersing the working and reference electrodes into the solvent system.
  • the auxiliary electrode may be isolated from the working electrode compartment during application of the electric potential, the mixture may be stirred, but such is not necessary.
  • the reaction takes place at room temperature and pressure under a blanket of inert gas.
  • an inert gas for example, N2, Ar
  • N2 inert gas
  • a potential of -0.45 V versus SCE in the DMSO solvent system using KBr as supporting electrolyte resulted in production of only the fullerene salts containing C60 monoanion. Since the potential necessary to produce the anions of desired valence is solvent dependent its value can be determined via cyclic volta - metry (CV) or differential pulse polarography (DPP). Care must be 6 -
  • the process of the present invention may be used to selec ⁇ tively generate the salt of the fullerene anions in solutions of the fullerenes and other hydrocarbons by applying a current to the solu ⁇ tion, wherein the current is of sufficiently low voltage to selective ⁇ ly reduce the particular fullerene to the correspondent salt of the fullerene anion without reducing the other hydrocarbons.
  • the fuller ⁇ ene anions have the formula C ⁇ -y, wherein C x is a fullerene, prefera ⁇ bly a fullerene selected from the group consisting of C ⁇ o and C70 and wherein y is an integer of from 1 to 3, specifically 1, 2 and 3.
  • the range of electric potentials will vary with the solvent system, but can readily be selected by one having ordinary skill in the art.
  • the electric potential is from about zero to about -0.7 V, when the fullerene anion is selected from the group consisting of C6o ⁇ l (when the fullerene is Ceo) and C70" 1 when the fullerene is C70; it is from about -0.80 V to about -1.1 V when the fullerene anion is selected from the group consisting of C ⁇ "2 (when the fullerene is C ⁇ o) and C7o * 2 (when the fullerene is C60) and C7o ⁇ 2 (when the fullerene is C70); and it is from about -1.3 V to about -1.7 V when the fullerene anion is selected from the group consisting of C ⁇ O" 3 (when the fuller ⁇ ene is C ⁇ o) and Z ⁇ ⁇ (when the fullerene is C70).
  • 60 ⁇ l > which is prepared from C ⁇ o at a potential of -0.70 V in 1:2 dichloromethane/toluene mixtures, may be selectively prepared as the salt of the C60 ⁇ l anion from mixtures of C60 with other hydrocarbons having higher potentials (that is, having a chemical inertness within the range of potentials at which the C ⁇ o" 1 anion is produced) by applying the foregoing chemical potentials to the solution.
  • the salt of the fullerene anion may be present in the solution or precipitated therefrom.
  • the actual voltage may vary, depending on the solvent in which the reduction is conducted.
  • the potential should be chosen within the range of the electrochemical potential necessary to generate the particular salt of the fullerene anion and within the range of chemical inertness for the other hydrocarbons. (For techni ⁇ cal details see, for example, P. T. Kissinger and Wm. H. Heine an, Editors, Laboratory Techniques in Electrochemistry-, Marcel Decker, Inc., N.Y. (1984); and A. Bard and L. Faulkner, Electrochemical Methods. Wiley and Sons, N.Y. (1980)).
  • the A n C product may be isolated by precipitation; for example, using a non-solvent or precipitating agent, such as toluene or ether or by reducing the volume of the solvent used via vacuum distillation or low temperature freezing.
  • a non-solvent or precipitating agent such as toluene or ether
  • reducing the volume of the solvent used via vacuum distillation or low temperature freezing Using this technique, only the fullerene salt precipitates.
  • KC1 is used as a source of potassium cation, only KC ⁇ n, not KC1 is precipitated. Only traces of chloride ions are detectable in the KC60 solid precipitate via scanning electron microscopy energy dispersive spectra technique.
  • the following examples are intended to demonstrate the invention and not l imit it in any way.
  • Example 1 The procedure specified in Example 1 was employed using C70 and produced the alkylammonium C70 *1 fulleride salt (Bu4N)+lC70" 1 , as shown by electrochemical and ESR analysis.
  • a polar solvent system consisting of a dimethyl sulfoxide DMSO/toluene solution (6/1 v/v) containing a suspension of 0.1 g C ⁇ o and 0.25 KC1 was electrolyzed at -0.45 V vs. SCE for a time sufficient to produce C60 ⁇ *- The solution turned red at the end of the reduc ⁇ tion. Addition of toluene (about 5:1 toluene/DMSO) and refrigeration overnight at -20°C allowed for the removal of most of DMSO and some toluene as a frozen solid.
  • Example 4 The procedure of Example 4 was repeated using KBr instead of KC1 to produce K+1C60 "1 fulleride salt.
  • This example illustrates the use of C ⁇ O as a solid state electrode component.

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Abstract

L'invention concerne de nouvelles compositions de matière ayant la formule AnCx, dans laquelle A représente un cation monovalent et Cx représente un anion de fullerène et de préférence dans laquelle x est égal à 60 et 70. L'invention concerne également un procédé de préparation de la composition par application d'un potentiel électrique à une solution non aqueuse d'un fullerène et d'un sel contenant un cation monovalent. De plus, l'invention concerne un procédé de production électrochimique de sels de fullerure sous la forme d'une solution dans d'autres hydrocarbures. En outre, l'invention concerne un procédé de préparation électrochimique de sels de fullerure solides. On peut utiliser les compositions comme matière d'électrode dans des piles électrochimiques réversibles, des supraconducteurs, des marques de spin, des thermomètres magnétiques, des précurseurs organiques et polymères.
PCT/US1992/010120 1991-11-26 1992-11-23 Nouveaux sels de fullerenes WO1993011067A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP93900639A EP0614444A4 (fr) 1991-11-26 1992-11-23 Nouveaux sels de fullerenes.
JP5510208A JPH07501782A (ja) 1991-11-26 1992-11-23 新規なフレレン類の塩

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US79839091A 1991-11-26 1991-11-26
US798,390 1991-11-26

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EP (1) EP0614444A4 (fr)
JP (1) JPH07501782A (fr)
AU (1) AU3223093A (fr)
CA (1) CA2124191A1 (fr)
WO (1) WO1993011067A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5811460A (en) * 1994-01-24 1998-09-22 The Regents Of The University Of California Water soluble fullerenes with antiviral activity
RU2119449C1 (ru) * 1997-04-24 1998-09-27 Институт нефтехимии и катализа с опытным заводом АН Республики Башкортостан Способ получения этилированных фуллеренов
RU2160226C2 (ru) * 1998-02-16 2000-12-10 Институт нефтехимии и катализа АН РБ Способ получения хлорпроизводных фуллерена c60
EP1199281A1 (fr) * 2000-10-20 2002-04-24 PIRELLI CAVI E SISTEMI S.p.A. Procédé de préparation d'un fullérènure métallique
RU2182897C1 (ru) * 2001-03-02 2002-05-27 Химический факультет МГУ Способ получения трифторметильных производных фуллеренов
RU2188154C2 (ru) * 2000-07-14 2002-08-27 Институт нефтехимии и катализа АН РБ и УНЦ РАН Способ получения фуллерен[60]сульфоксидов
RU2243298C2 (ru) * 1999-05-04 2004-12-27 Пирелли Кави Э Системи С.П.А. Способ получения сверхпроводящего слоистого материала и получаемый из него сверхпроводящий слоистый элемент
EP2322475A1 (fr) * 2009-11-17 2011-05-18 Siemens Aktiengesellschaft Procédé de synthèse de fulleride de nanoagrégats métalliques et matériau comportant un fulleride de nanoagrégats métalliques
CN109053468A (zh) * 2018-07-03 2018-12-21 苏州大学 一种富勒烯三丙二酸铵衍生物、制备方法及其应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08501524A (ja) * 1992-09-16 1996-02-20 ヘキスト・アクチェンゲゼルシャフト フラレンの分離方法

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
Journal of American Chemical Society, Vol. 113(11), 22 May 1991, "Spectrochemical Study of C60 and C70 Fullerenes and their Mono-, Di-, Tri- and Tetraanions", see Figure 1. *
Journal of American Chemical Society, Vol. 113(20), 25 September 1991 (DuBOIS et al.), "Electrochemical Detection of Fulleronium and Highly Reduced Fulleride (C605-) Ions in Solution", see Figure 2. *
Journal of American Chemical Society, Vol. 113(3), 30 January 1991 (ALLEMAND et al.), "Two Different Fullerenes Have the Same Cyclic Voltammetry", see Figure 2. *
Journal of American Chemical Society, Vol. 113(8), 10 April 1991 (BAUSCH et al.), "Diamagnetic Polyanions of the C60 and C70 Fullerenes: Preparation, 13C and 7Li NMR Spectroscopic Observation, and Alkylation with Methyl Iodide to Polymethylated Fullerenes", see Footnote 10. *
Journal of Chemical Physics, Vol. 88(3), 01 February 1988 (COX et al.), "Carbon Clusters Revisited: The 'Special' Behavior of C60 and Large Carbon Clusters", see pages 1595-1596. *
Nature, Vol. 350, 28 March 1991 (HADDON et al.), "Conducting Films of C60 and C70 by Alkali Metal Doping", see Abstract. *
See also references of EP0614444A4 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5811460A (en) * 1994-01-24 1998-09-22 The Regents Of The University Of California Water soluble fullerenes with antiviral activity
US6204391B1 (en) 1994-01-24 2001-03-20 The Regents Of The University Of California Water soluble fullerenes with antiviral activity
US6613771B2 (en) 1994-01-24 2003-09-02 The Regents Of The University Of California Method of treatment of viral infection including HIV using water soluble fullerenes
RU2119449C1 (ru) * 1997-04-24 1998-09-27 Институт нефтехимии и катализа с опытным заводом АН Республики Башкортостан Способ получения этилированных фуллеренов
RU2160226C2 (ru) * 1998-02-16 2000-12-10 Институт нефтехимии и катализа АН РБ Способ получения хлорпроизводных фуллерена c60
RU2243298C2 (ru) * 1999-05-04 2004-12-27 Пирелли Кави Э Системи С.П.А. Способ получения сверхпроводящего слоистого материала и получаемый из него сверхпроводящий слоистый элемент
RU2188154C2 (ru) * 2000-07-14 2002-08-27 Институт нефтехимии и катализа АН РБ и УНЦ РАН Способ получения фуллерен[60]сульфоксидов
EP1199281A1 (fr) * 2000-10-20 2002-04-24 PIRELLI CAVI E SISTEMI S.p.A. Procédé de préparation d'un fullérènure métallique
RU2182897C1 (ru) * 2001-03-02 2002-05-27 Химический факультет МГУ Способ получения трифторметильных производных фуллеренов
EP2322475A1 (fr) * 2009-11-17 2011-05-18 Siemens Aktiengesellschaft Procédé de synthèse de fulleride de nanoagrégats métalliques et matériau comportant un fulleride de nanoagrégats métalliques
US8734752B2 (en) 2009-11-17 2014-05-27 Siemens Aktiengesellschaft Method of synthesis of a fulleride of metal nano-cluster and material comprising a fulleride of metal nano-cluster
RU2553894C2 (ru) * 2009-11-17 2015-06-20 Сименс Акциенгезелльшафт Способ синтеза фуллерида металлического нанокластера и материал, включающий фуллерид металлического нанокластера
CN109053468A (zh) * 2018-07-03 2018-12-21 苏州大学 一种富勒烯三丙二酸铵衍生物、制备方法及其应用
CN109053468B (zh) * 2018-07-03 2020-12-15 苏州大学 一种富勒烯三丙二酸铵衍生物、制备方法及其应用

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JPH07501782A (ja) 1995-02-23
EP0614444A4 (fr) 1995-03-15
EP0614444A1 (fr) 1994-09-14
AU3223093A (en) 1993-06-28
CA2124191A1 (fr) 1993-06-10

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