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2006 | Buch

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Natural Fullerenes and Related Structures of Elemental Carbon

verfasst von: Frans J. M. Rietmeijer

Verlag: Springer Netherlands

Buchreihe : Developments in Fullerene Science

Enthalten in: Springer Professional "Wirtschaft+Technik" , Springer Professional "Technik"

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Über dieses Buch

Observational, experimental and analytical data show that C60, larger fullerenes, and related structures of elemental carbon exist in interstellar space, meteorites, and on Earth and are associated with meteorite in impact events and in carbon-rich environments such as coals (shungite) and bitumen. The existence of natural fullerenes is at best contested and incompletely documented; realistically it is still controversial. Their presence in astronomical environments can be experimentally constrained but observationally they remain elusive. Fullerenes formation in planetary environments is poorly understood. They survived for giga-years when the environmental conditions were exactly right but even then only a fraction of their original abundance survived. Natural fullerenes and related carbon structures are found in interstellar space, in carbonaceous meteorites associated with giant meteorite impacts (including at the Cretaceous-Tertiary boundary) as well as in soot, coal and natural bitumen.

This book provides an up-to-date summary of the state of knowledge on natural fullerenes occurrences and the laboratory techniques used to determine their presence at low concentration in rock samples. It demonstrates that natural fullerenes exist and should be searched for in places not yet considered such as carbon-containing deep-seated crustal rocks.

Natural Fullerenes and Related Structures of Elemental Carbon is written for professional astronomers, meteoriticists, earth and planetary scientists, biologists and chemists interested in carbon and hydrocarbon vapor condensation. It is an invaluable resource for practicing research scientists and science teachers in Earth and Planetary Science, Astronomy and Carbon Science.

Inhaltsverzeichnis

Frontmatter

Chapter 1. Introduction: Space - Pandora’s Box

Harold Kroto

Chapter 2. Formation of Fullerenes

Abstract

To gain information on fullerene formation, the production methods based on the evaporation of graphite are outlined. In particular, the effects of the buffer gas temperature are considered in connection with experiments performed with a laser furnace arrangement. In addition, fullerene formation by incomplete combustion and by pyrolysis is discussed. The former method is presently applied for large-scale fullerene production and very likely is also the source of most of the fullerenes occurring on earth. The formation processes based on evaporation and on combustion seem to be vastly different indicating that various chemical reaction routes lead to fullerenes.

Wolfgang Krätschmer

Chapter 3. Carbonaceous Onion-Like Particles: A Possible Component of the Interstellar Medium

Abstract

A carbonaceous material formed from a hydrocarbon plasma called quenched carbonaceous composite (QCC) is shown to have functional groups that approximate the positions of the interstellar 217.5 nm absorption and the infrared emission features at 3.3—11.3 μm. A form of this material, called “dark-QCC” has abundant carbonaceous onion-like particles. We present the results of various experiments involving QCC and conjecture that the carbonaceous onion-like particles in QCC may be a good laboratory analog to the carrier of the interstellar absorption and emission features. A scenario for dust formation from carbonaceous onion-like particles is presented.

Setsuko Wada, Alan T. Tokunaga

Chapter 4. Fullerenes and Related Carbon Compounds in Interstellar Environments

Abstract

The prediction of the existence of the fullerene C₆₀ and its subsequent isolation from soot produced a large interest for fullerenes in the astronomical community. Fullerenes of astronomical origin have only been detected in meteorites and associated with an impact crater on the Long Duration Exposure Facility spacecraft. The discovery of fullerenes led to the hypothesis that they may be stable carbon molecules present in interstellar space. Many authors have suggested the possible presence of C60 and carbon onions in astrophysical environments as well as their relation to the diffuse interstellar bands (DIBs) and the UV bump at 220 nm in the interstellar extinction curve. As first evidence for the largest molecule ever detected in space, two diffuse interstellar bands (DIBs) have been identified in the near infrared that are consistent with laboratory measurements of the C60 cation. We review the current knowledge on fullerenes in space and present new observations of the interstellar bands at 957.7 nm and 963.2 nm.

Pascale Ehrenfreund, Nick Cox, Bernard Foing

Chapter 5. Natural C60 and Large Fullerenes: A Matter of Detection and Astrophysical Implications

Abstract

Fullerene was theoretically predicted and experimentally discovered, but its detection in laboratory studies is still underrepresented with respect to its theoretical abundance. Recent High Resolution Transmission Electron Microscopy (HRTEM) studies of soot samples, however, lead to single fullerene molecule detection in higher amounts than was previously established. HRTEM is able to identify fullerenes even if they are only present in small quantities that would be below the detection limit of chemical techniques. Fullerenes will probably remain largely undetected until higher signal to noise ratio measurements are used to search for them. Such studies could yield different conclusions on fullerene abundances both in terrestrial and in extraterrestrial samples. For the latter, important astrophysical implications have to be considered.

Alessandra Rotundi, Frans J. M. Rietmeijer, Janet Borg

Chapter 6. Fullerenes in Meteorites and the Nature of Planetary Atmospheres

Abstract

We address the hypothesis that fullerenes are an important carrier phase for noble gases in carbonaceous chondrite meteorites. Unlike other proposed carbon carriers, nanodiamond, SiC, graphite and phase Q, fullerenes are extractable in an organic solvent. It is this unique property, in fact, this may be why fullerene molecules or fullerene-related compounds were overlooked as a carrier phase of noble gases in meteorites. To further evaluate how fullerenes trap noble gases within their closed-cage structure, we compared the natural meteorite fullerenes to synthetic “Graphitic Smokes” soot. High Resolution Transmission Electron Microscopy used to directly image the fullerene extracted residues clearly showed that C₆₀ and higher fullerenes, predominantly C > 100, are indeed the carrier phase of the noble gases measured in the Tagish Lake, Murchison and Allende carbonaceous chondrite meteorites, and synthetic “Graphitic Smokes” material. The implication for the role of fullerenes, which trap noble gases condensed in the atmosphere of carbon-rich stars, is that the true nature of terrestrial planetary atmospheres is presolar in origin. Fullerene, like other carbon carriers, were then transported to the solar nebula, accreted into carbonaceous chondrites and delivered to the terrestrial planets.

Luann Becker, Robert J. Poreda, Joseph A. Nuth, Frank T. Ferguson, Feng Liang, W. Edward Billups

Chapter 7. Fullerenes and Nanodiamonds in Aggregate Interplanetary Dust and Carbonaceous Meteorites

Abstract

If fullerenes are a common carbon phase in circumstellar dust and the presolar dust of the dense molecular wherein our solar system had formed, they should be present in the most primitive samples that still contain the vestiges of the accreting dust in the solar nebula 4.56 Ga ago. Such dust would be expected to have survived in comet nuclei and in the most primitive asteroids. They would be represented by collected chondritic, aggregate, interplanetary dust particles. As yet, there is no evidence of fullerenes in these particles but C₆₀ and higher fullerenes are present in several carbonaceous chondrite meteorites. Metastable fullerenes may not survive the complex natural processing of comet and asteroid debris in the parent body, during solar system sojourn and atmospheric entry and laboratory storage. The possibility of fullerene modification to nanodiamonds in primitive asteroids is discussed.

Frans J. M. Rietmeijer

Chapter 8. Fullerenes and Related Structural Forms of Carbon in Chondritic Meteorites and the Moon

Abstract

Reports concerning the presence or absence of fullerenes in chondritic meteorites are reviewed. Structural forms of carbonaceous matter in these meteorites are discussed in the context of fullerene formation.

Dieter Heymann, Franco Cataldo, Marie Pontier-Johnson, Frans J. M. Rietmeijer

Chapter 9. Fullerenes in the Cretaceous-Tertiary Boundary

Abstract

Fullerenes C₆₀ and C₇₀ were found in the thin clay seams of nine worldwide locations of the geologic boundary between the Cretaceous and Tertiary periods. These clays are also rich in soot. One hypothesis suggests that the fullerenes were synthesized in global wildfires that followed the meteorite impact 65 Ma ago. An alternative hypothesis suggests that the fullerenes predate the formation of the solar system because they contain isotopically anomalous helium in their carbon cages.

Dieter Heymann, Wendy S. Wolbach

Chapter 10. Fullerene C60 in Solid Bitumen Accumulations in Neo-Proterozoic Pillow-Lavas at Mítov (Bohemian Massif)

Abstract

Fullerene C₆₀ occurs at extremely low concentration (0.2—0.3 ppm) in hard solid bitumen that was accumulated in the pillow lava bodies exposed at Mítov (Teplá-Barrandian Neo-proterozoic of the Bohemian Massif). No higher fullerenes were documented. The C₆₀ fullerene and its precursors are present in non-graphitic and non-graphitizable carbonaceous matter. Inclusions of fullerene are found embedded within glass-like carbons that are found within the pillow lava bodies. Rare fullerenes in Mítov were probably preserved in the closed micropores and mesopores of the glass-like, solid bitumen. Pyrolysis of biogenic PAHs precursors seems a plausible way to form fullerenes in geological environments.

Jan Jehlička, Otakar Frank

Chapter 11. Fullerene Synthesis by Alteration of Coal and Shale by Simulated Lightning

Abstract

A graptolitic shale, a metamorphosed black schist and a bituminous coal with different organic carbon content but without detectable amounts of fullerenes were subjected to high-energy electric impulses of current amplitudes comparable to those of natural lightning strikes that could lead to the formation of fulgurites. The search for fullerenes concentrated on rock surfaces altered during the impulse experiment using Fourier transform infrared spectroscopy (FTIR). Toluene-extractable materials from the altered zones were investigated by high-performance liquid chromatography (HPLC) and electron-impact ionization mass spectroscopy (EIMS). Powders from altered surfaces were also analyzed by laser desorption time-of-flight mass spectroscopy. Two of four characteristic C₆₀ FTIR peaks were only observed in one piece of black schist. As no C60 fullerene was detected by HPLC and EIMS in this modified sample, we find no evidence that electric impulse-induced fullerenes were present in any samples. We discuss how the physicochemical conditions in our lightning-strike simulation experiments could have contributed to failure to produce fullerenes in rocks that are rich in organic carbon. Our results underscore the apparent paucity of natural fullerenes induced by lightning strikes.

Ota Frank, Jan Jehlička, Věra Hamplová, Aleš Svatoš

Chapter 12. Fullerene in Some Coal Deposits in China

Abstract

Highly variable concentrations of natural C60 are reported from several coals from mines in the Yunnan-Guizhou provinces and the Inner Mongolia-Shanxi- Xinjiang provinces of China. The fullerene-extraction procedures from coals and C₆₀ identification by Fourier Transform Infrared spectroscopy are described.

P. H. Fang, Fawen Chen, Ruzhao Tao, Binghou Ji, Chongjun Mu, Ergang Chen, Yuanjian He

Chapter 13. Biogenic Fullerenes

Abstract

This paper presents the hypothesis that algal remains were precursors of the fullerenes in the hard carbonaceous rock Shungite (Russia), in carbonaceous matter from the hard rocks of the Black Member of the Onaping Formation at Sudbury (Canada), and in solid, hard bitumens from Mitov (Czech Republic). The paper argues further that PAHs from the biogenic matter were transformed, perhaps by cyclomerization followed by zip-up, during the geologic metamorphic stages experienced by these rocks.

Dieter Heymann

Chapter 14. Future Procedures for Isolation of Higher Fullerenes in Natural and Synthetic Soot

Abstract

We describe the extraction methodologies for the isolation of fullerenes in synthetic “Graphitic Smokes” soot. These same methods were used to isolate natural fullerenes in some carbonaceous chondrite meteorites and in meteor impact-related sedimentary deposits previously described in the literature. In addition, a new functionalizatoin methodology that significantly enhances the yield of fullerenes extracted in synthetic fullerene material (up to 20% fullerene) will be discussed. Both laser desorption-mass spectrometry and high-resolution transmission electron microscopy were used to characterize fullerenes extracted from the synthetic soot. These extraction methods promise to reveal new insights on the encapsulaton of noble gases in a variety of fullerene and fullerene-related structures up to C₁₀₀₀.

Luann Becker, Robert J. Poreda, Joseph A. Nuth, Frank T. Ferguson, Feng Liang, W. Edward Billups

Titel: Natural Fullerenes and Related Structures of Elemental Carbon
verfasst von: Frans J. M. Rietmeijer
Verlag: Springer Netherlands
Electronic ISBN: 978-1-4020-4135-8
Print ISBN: 978-1-4020-4134-1
DOI: https://doi.org/10.1007/1-4020-4135-7

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