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WO1993019007A1 - Fullerenes metastables - Google Patents

Fullerenes metastables Download PDF

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Publication number
WO1993019007A1
WO1993019007A1 PCT/US1992/007491 US9207491W WO9319007A1 WO 1993019007 A1 WO1993019007 A1 WO 1993019007A1 US 9207491 W US9207491 W US 9207491W WO 9319007 A1 WO9319007 A1 WO 9319007A1
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WIPO (PCT)
Prior art keywords
fullerene
isomer
metastable
fullerenes
molecular formula
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PCT/US1992/007491
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English (en)
Inventor
Jack B. Howard
Arthur L. Lafleur
Michael A. Quilliam
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Massachusetts Institute Of Technology
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Publication of WO1993019007A1 publication Critical patent/WO1993019007A1/fr

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    • 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
    • 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

Definitions

  • the present invention relates to dosed-caged carbon molecules known as Buckminsterfullerenes or fullerenes and isomers thereof.
  • Fullerenes were first reported by Kroto et al. in carbon vapor produced by laser irradiation of graphite ((Nature 318, 162-164 (1985)).
  • Fullerene C M is a closed cage carbon structure containing 20 six-membered rings and 12 five- membered rings with the appearance of a soccer ball. There has been a surge of scientific interest in these compounds because they represent a new class of carbon in addition to the two known forms, graphite and diamond.
  • Fullerenes have many potential applications. The ability to intercalate metal cations into the structure suggests uses as catalysts in industrial processes.
  • the potassium-fullerene C ⁇ is a superconductor with a T c of 11 K.
  • the fullerene C ⁇ , surface is susceptible to chemical reactions such a hydrogenation and fluorination. Fluorinated fullerenes are expected to be good lubricants.
  • Diederich et al. (Science 254, 1768-1770(1991) reported the isolation and characterization of isomeric C ⁇ fullerenes. However, isomeric forms of lower fullerenes are unknown, in particular, C x , where x is less than 78.
  • metastable as that term is used herein, it is meant a species that is transient but of sufficient stability to permit isolation under specific conditions.
  • the molecular formula of the metastable fullerene is o- In other preferred embodiments, the molecular formula of the metastable fullerene is Q.
  • the metastable fullerene converts to a fullerene having the same molecular formula upon heating.
  • isolated pentagon rule requires that no two pentagonal carbon sub-units of closed- cage structure lie adjacent to one another. Metastability may be the result of having adjacent pentagonal carbon sub-units in the isomeric fullerene.
  • a fullerene isomer having M + and M +2 ions identical to that of a stable fullerene and further having a retention time in liquid chromatography differing from that of the fullerene having the formula C x .
  • M + and M +2 ions as that term is used herein, it is meant the singly and doubly charged parent ion peaks identified upon mass spectroscopic analysis.
  • isomer as that term is used herein, it is meant a structural or conformational variation of a compound having the same molecular formula as the known fullerenes. Isomers of C 60 , C 70 , C 76 , C ⁇ , Gr ⁇ and C 94 have been isolated and characterized. However, it is recognized that isomers of other fullerenes, particularly of higher molecular weight, are produced.
  • the fullerene isomer is metastable. Isomers of fullerene C 60 were considered to be unlikely in view of the fact that the known "soccer ball" structure which possesses 12 five- membered or pentagonal rings completely surrounded by the 20 six-membered or hexagonal rings is the only possible arrangement which obeys the "isolated pentagon rule".
  • the yield of a metastable isomer can be optimized in any fullerene source by rapidly quenching the fullerenes at a location in the process where the fullerenes are being produced.
  • metastable isomer yield is improved by avoiding high temperatures in post-production treatments.
  • the metastable fullerene converts readily under the high temperature conditions of the flame. By quenching the reaction before there is sufficient time to allow the complete conversion of the metastable to the stable fullerene, the yield of metastable fullerene is enhanced.
  • Means of quenching include, but are not limited to, inserting a collection tube near the location of fullerene formation into which is introduced the cold nitrogen evaporant from liquid nitrogen source or by injecting a fluid from high velocity jets into the location of fullerene production.
  • Analysis of materials made by the process disclosed in the parent application indicate the presence of isomers of C 60 and C 70 fullerenes. In the purification of soot samples by high performance liquid chromatography (HPLC), species were observed with retention times differing from those of the o and C 70 fullerenes.
  • Figure 1 is a high performance liquid chromatogram (HPLC) of a toluene extract of a flame soot indicating C 60 and C 70 as well as new peaks A- D;
  • HPLC high performance liquid chromatogram
  • Figure 2 is selected ion chromatograms (SIC) from the HPLC-MS analysis of a flame soot;
  • Figure 3 is a background-subtracted positive mass spectra obtained at the crests of chromatographic peaks annotated in Figure 2;
  • Figure 4 is a background-subtracted negative ion mass spectra obtained at the crests of chromatographic peaks annotated in Figure 2;
  • Figure 5 illustrates the time-dependence of chromatographic peak areas from HPLC analysis of flame-derived fullerene extract in boiling toluene under argon.
  • PACs of high molecular weight, by HPLC or supercritical fluid chromatography (SFC) coupled directly to mass spectrometry (LC-MS or SFC- MS), have been developed recently. These methods employ either a moving- belt interface with flash heating of the analyte as it enters the El source, or a heated pneumatic nebulizer coupled to an atmospheric pressure chemical ionization (APCI) source in which electron transfer to benzene molecular cations is arranged to be the dominant ionization mechanism. In the present work the flame soot samples were analyzed by these complementary LC-MS techniques, as well. as by HPLC interfaced on-line to a diode array detector for UN spectroscopy. Experimental.
  • APCI atmospheric pressure chemical ionization
  • HPLC with UV spectroscopy The column used was 25cm long x 2.1 mm i.d., with Vydac 201TP C lg packing.
  • the initial solvent was 100% acetonitrile for 5 min, then programmed linearly to 100% dichloromethane over 45 min, held for 5 min, then programmed back to initial composition over 5 min.
  • the mobile phase flow rate was 200 uL/min, with an injection volume of 5 ⁇ L.
  • a HP1090M liquid chromatograph Hewlett Packard Co.,Palo Alto, CA, USA), equipped with a binary DR5 solvent delivery system, a HP1040A diode array detector, and a HP7994A data system, was used in all LC-UN analyses.
  • the detector was configured for continuous full UN scan acquisition (220-600 ran). HPLC with on-line mass spectrometry. The HPLC conditions were identical to those used in the LC-UV analyses. In one set of experiments the HPLC effluent (no split) was introduced to an electron ionization mass spectrometer (VG 20-250 quadrupole mass filter, NG Mass Lab, Altrincham, U.K.) via a NG moving belt interface. The conditions used were similar to those for LC-MS analysis of PACs with molecular weights of up to 600, except that the fullerenes and related compounds required higher temperatures for efficient volatilization. The nominal electron energy was 70 eN, with a trap current of 100 ⁇ A.
  • the source temperature was 350°C, and the flash belt heater at the tip of the belt interface, located within the body of the ion source, was operated at maximum power (belt surface temperature unknown). In addition, the belt dean-up heater (also at maximum power) and wash-bath had to be employed in order to avoid memory effects.
  • a NG 11-250J data system was used for instrument control and for data acquisition and processing.
  • the LC-MS experiments employing electron transfer APCI were conducted using an API m triple quadrupole instrument (SCIEX, Thornhill, Ontario), equipped with a heated pneumatic nebuliser interface (SCIEX).
  • the pneumatic nebuliser is contained within a concentric quartz heating tube, itself located within the room temperature APCI source; the indicating thermocouple is located on the exterior surface of this heating tube, together with the heating element.
  • Ionization was achieved in a fashion very similar to that described for SFC-MS analysis of PACs.
  • the APCI plasma was sustained by a cold corona discharge (stainless steel needle maintained at 3 kN).
  • Introduction of benzene vapor via the nebulizing gas inlet ensured that the dominant positive reactant ions in the plasma were C 6 H 6 + -, together with some water cluster ions from residual water in the system.
  • the predominant ionization mechanism for polycyclic aromatic hydrocarbons (PAHs) involves electron transfer to C 6 H 6 + -, with some tendency for protonation. Characterization of this APCI plasma in the absence of analytes also showed a significant population of benzene-derived ions at m/z 91, presumably C 7 H 7 + ions of tropylium structure.
  • Peaks B and C os C ⁇ and C 70 species were of particular interest since they were absent from the chromatogram of extract of soot from resistive heating of graphite.
  • the UV spectra obtained at the crests of Peaks B and C differ from those of the authentic C 60 and C 70 fullerenes (Peaks I and II), but do have fullerene-like characteristics.
  • the El mass spectra acquired in the moving-belt LC-MS experiments at the crests of peaks B and C were identical to those for peaks I and II respectively, showing intense M + - and M 2+ ions with appropriate isotopic distributions. This combined UN and El evidence strongly suggested that peaks B and C arose from isomers of the C 60 and ,, fullerenes.
  • thermal decomposition of labile fullerene adducts to the parent compounds, subsequent to chromatographic separation and during the volatilization from the moving belt (several hundreds of °C at the belt-tip heater inside the ion source) prior to ionization, could not be excluded.
  • HPLC-MS coupling was required. This was achieved using an APCI source, similar to that used for SFC-MS analyses of PACs.
  • the HPLC effluent was nebulized to micron- sized droplets within a heated quartz tube; the maximum gas temperature in this region was about 110°C in the first experiments, later reduced to 80- 90°C with no significant change in the results obtained.
  • the mobile phase was rapidly evaporated from these droplets via interactions with the heated gas (nitrogen saturated with benzene vapor, together with vaporized mobile phase), leaving extremely small particles each containing only a few analyte molecules.
  • the vapor pressure of such small particles can be many times larger than that of the bulk material, permitting vaporization of analytes which are thermally labile when heated in the bulk phase.
  • the vaporized sample was then drifted into a cold corona-discharge plasma, whose composition was controlled by manipulating that of the atmosphere in the APCI source.
  • addition of benzene ensured that the dominant mechanism for formation of positive ions from the sample was electron transfer to H 6 + - ions, whose recombination energy is 9.25 eN. Since the ionization energy of C ⁇ ( ) is about 7.8 eN, electron transfer ionization was efficient and the excess energy of 1.5 eN was readily degraded by collisions with the atmosphere.
  • a minor ionization mechanism was formation of adducts with tropylium ions (C 7 H 7 + , m/z 91) formed from benzene in the APCI plasma.
  • the sample-derived ions thus transmitted to the mass analyzer were internally cold, yielding mass spectra which exhibit only molecular and adduct ions with little or no fragmentation.
  • Peak B the spectrum obtained for Peak B is almost identical to that for Peak I (the authentic C 60 fullerene), further supporting the present contention that Peak B corresponds to a chromatographically distinguishable form of C 60 rather than to some adduct of C 60 which, subsequent to ionization, fragments immediately to yield a mass spectrum which is identical to that formed directly from ionization of the authentic fullerene.
  • Slight differences between the two spectra in Fig. 4 are due mostly to differences between the compositions of the APCI plasma in the two cases, under the HPLC gradient conditions used in these LC-MS experiments.
  • Peak D corresponds to C ⁇ (Fig. 2f).
  • the two minor non-annotated peaks preceding Peak D correspond to C 76 (Fig.s 2e and 3c); a chiral form of C 76 was isolated and characterized very recently by Diederich et al. Evidence was also obtained (not shown) for several forms of G ⁇ , and ⁇ , present at very low abundances in this extract. Note that the mass spectra obtained for these minor components, e.g. Fig. 3c, were obtained near the ion statistical limit so that significant random deviations of the isotope intensity distributions, from those predicted from assumed molecular formulae, were observed.
  • Peak A (Fig. 1) was identified as a monoxide C 60 O via the APCI mass spectrum, which showed evidence for increased importance of protonation to form (M + H) + (Fig. 3d) relative to that of the C 60 compounds.
  • the SIC for m/z 736 (Fig. 2b) shows evidence for at least 5 chroma tographically distinguishable species giving rise to C 60 O + ', but two of these have retention times identical to those of peaks B and I and were probably formed as oxidation artifacts of the corresponding carbon clusters in the APCI plasma.
  • FIG. 2b correspond to monoxides of less symmetrical C 60 isomers not present in the graphite soot.
  • Fig. 2d shows similar evidence for several QO isomers in the flame soot, apart from the APCI artifacts.
  • the corresponding experiment on the graphite soot extract showed evidence for only two QO compounds apart from the APCI artifact at a retention time corresponding to Peak II; this observation is again qualitatively consistent with the requirement that the new C 70 isomers (Fig. 2c) possess a lower degree of molecular symmetry than does the authentic fullerene.
  • One C 70 O compound has been isolated previously 14 from a soot produced by resistive heating of graphite.
  • Peak B new C 60 isomer
  • Peak I authentic C fe0 fullerene
  • Fig. 5 the sum of the two intensities as a function of time. This could be due in part to a higher integrated molar absorption for the new isomer (Peak B) than for its fullerene counterpart, or to possible side-reactions.
  • a small but significant rise (Fig. 5) in the intensity of Peak A (C 60 O) suggests that some degree of oxidation occurred despite the precautions taken. Also, other processes such as polymerization would have yielded side-products which would not have been detected in these experiments.

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Abstract

On a identifié et isolé des fullerènes métastables, particulièrement des isomères des formes stables des fullerènes C60 et C70. Les fullerènes métastables se transforment en fullerènes de même poids moléculaire par chauffage. On a isolé et identifié un isomère de fullerène. Il comporte des ions M+ et M+2 identiques à ceux d'un fullerène de formule C¿x? où x varie entre 60 et 75, et sa durée de rétention relative à la chromatographie en phase liquide diffère de celle des fullerènes de formule Cx.
PCT/US1992/007491 1992-03-18 1992-09-04 Fullerenes metastables WO1993019007A1 (fr)

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US855,802 1992-03-18

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7189681B2 (en) * 2000-12-22 2007-03-13 Nec Corporation Superconducting material and method for producing the same
DE10296273B4 (de) * 2001-02-10 2009-01-29 Seoul National University Industry Foundation Verfahren zum Herstellen schalenförmiger feiner Kohlenstoffteilchen

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
Chemical Abstracts, vol. 115, no. 14, 7 October 1991, (Columbus, Ohio, US), C. COULOMBEAU et al.: "Study of 74 C60 carbon isomer aggregates by the Hueckel method", see page 435, abstract no. 142838w, & J. CHIM. PHYS. PHYS.-CHIM. BIOL. 1991, 88(5), 665-74 *
Chemical Abstracts, vol. 116, no. 8, 24 February 1992, (Columbus, Ohio, US), L. GOODWIN: "Structure and stability of some fullerene C60 isomers", see page 546, abstract no. 67712r, & PHYS. REV. B: CONDENS. MATTER 1991, 44(20), 11432-6 *
Chemical Abstracts, vol. 117, no. 8, 24 August 1992, (Columbus, Ohio, US), J.B. HOWARD et al.: "Production of C60 and C70 fullerenes in benzene-oxygen flames", see page 856, abstract no. 82176h, & J. PHYS. CHEM. 1992, 96(16), 6657-62 *
Chemical Physics Letters, vol. 184, no. 4, 27 September 1991, (Amsterdam, NL), A. GOERES et al.: "On the nucleation mechanism of effective fullerite condensation", pages 310-317 (cited in the application) *
Journal of the American Chemical Society, vol. 110, no. 4, 1988, (Washington, DC, US), T.G. SCHMALZ et al.: "Elemental carbon cages", pages 1113-1127 (cited in the application) *
Nature, vol. 352, 11 July 1991, (London, GB), J.B. HOWARd et al.: "Fullerenes C60 and C70 in flames", pages 139-141, see page 140, left-hand column, paragraph 1; figure 2 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7189681B2 (en) * 2000-12-22 2007-03-13 Nec Corporation Superconducting material and method for producing the same
DE10296273B4 (de) * 2001-02-10 2009-01-29 Seoul National University Industry Foundation Verfahren zum Herstellen schalenförmiger feiner Kohlenstoffteilchen

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