Fullerene-Like Carbon in Nature

and Perspectives of its use

in Science-Based Technologies
Vladimir V. Kovalevski
Carbon plays an all-important role in nature. Carbon atoms can to form complicated
organic networks some of those are base for existence of known forms of life. Ele-
mental carbon also shows very complicated behavior forming a number of different
structures. Recent years have been marked by an accented interest of scientists in
fullerenes, nanotubes and many nano-sized shapes (Kroto et al., 1985; Iijima, 1991).
Non-crystalline fullerene-like carbon forms were additionally obtained using an
arc discharge, ame, laser pyrolysis (Chhowalla et al., 1997; Mordkovich, 2000;
Grieco et al., 2000), and were even found in petrol soot (Lee et al., 2002). The
term fullerene-like has been used for roughly spherical carbon structures such as
carbon onions and hollow nanoparticles consisting of concentric curled carbon
layers. Some authors have specied additional characteristics such as a diameter
between ca. 5 and 20 nm (Chhowalla et al., 1997) and a lattice spacing of approxi-
mately 0.35 nm (Grieco et al., 2000). They infer the curling of graphene layers re-
sults from the presence of pentagonal rings as in fullerenes (Grieco et al., 2000).
Other authors assume that four- and eight-membered carbon rings can occur in
fullerene structures (Slanina et al., 1999). In addition, it has been hypothesized that
the graphene layers contain defects in the form of pentagonal, heptagonal, or other
kind of rings, singly or in combination, that affect the graphene-layer curvature and
create different fullerene-like structures (Cataldo, 2002).
Fullerenes and fullerites have been found in the natural environment (Buseck
et al., 1992; Becker et al., 1994; Novgorodova, 1999). Even more intriguingly, the
symmetry and shapes of icosahedral viruses, Murine leukemia virus, for instance,
are directly related to symmetries of giant fullerenes (Nermut and Mulloy, 2007).
Much natural free carbon occurs in the amorphous state in varieties that have long
been of interest because of their intriguing range in structures, properties, and indus-
trial applications. An interesting type of non-crystalline carbon occurs in the shun-
gite rocks of Karelia (Russia) (Shungites of Karelia, 1975; Buseck et al., 1997), from
Vladimir V. Kovalevski
Institute of Geology, Karelian Research Center, Russian Academy of Sciences, Pushkinskaya
St. 11, Petrozavodsk 185610, Russia, e-mail: kovalevs@krc.karelia.ru
165
166 V.V. Kovalevski
which the rst natural occurrence of fullerenes was reported (Buseck et al., 1992)
and hollow nanospheres and bers were described (Kovalevski et al., 1996). Shun-
gite rocks have simple mineral composition, which may contain shungite, quartz,
mica, carbonates and traces of other minerals. Shungite has chemical composition
consisting of C with traces of N, O, H and S. All types of these rocks have very
variable physico-chemical properties depending on the shungite structure, C con-
tent, the composition and characteristics of minerals and distribution of carbon and
minerals in these shungite rocks. For example, type I rocks have a relatively low
specic gravity (1.82.0 g/cm
3
), high electric conductivity (about 100 S/cm), and
some types have unusually high specic surface areas (up to 500 m
2
/g) as measured
by the (BET) adsorption of gaseous nitrogen. Carbon from shungite rocks demon-
strates fullerene-like signs on different structural and physical levels.
All high-resolution transmission electron microscopy (HRTEM) images of the
samples contain well-dened fringes, and these occur in packets of 514 sheets.
Many of these sheets are curved, and in places they appear as if they might close
upon themselves, although the tangle of intervening sheets makes such an interpre-
tation uncertain. The centers of the curved sheets may represent pores, consistent
with the high surface areas inferred from BET measurements. The STEM images
of shungites suggest 3-dimensional shells or, more commonly, fractions of such
shells or regions of graphene structure, that are highly disordered in bent stacks.
The 3-dimensional structures that might be surmised from the HRTEM images are
conrmed by the sets of nanodiffraction patterns. The strengths and directions of the
00l lines of spots correspond to sets of 0.34 nm fringes in the images. The ellipticity
of the rings suggests tilts of the sheets, which are apparently bent into 3-dimensional
shapes approximating closed or partly closed shells of rather irregular cross section.
In that sense it may be described on the permolecular level as a fullerene-like carbon
(Kovalevski et al., 2001).
There are two types of imperfections on the molecular level connected with irreg-
ularities of 100 fringes that suggest a disorder of the graphene layers from HRTEM
images. The former are connected with essential disorder of fringes that can re-
sulted from the presence of impurity atoms or clusters in the stack of graphene
layers. Other imperfections connected with insignicant disorder in the direction
of fringes and the distance between them, and can result from point defects or the
four-, ve-, eight-membered or other carbon rings that are signs of fullerene-like
structures (Cataldo, 2002).
The electron energy loss spectroscopy (EELS) of shungites provides information
on the electronic structure that is very sensitive to the valency, coordination, and
site symmetry of carbon atoms and is right dealing with structure-property relation-
ships. In the low-energy-loss region, two characteristic plasmon peaks occur: one
is the -plasmon corresponding to transitions between the and

states located
at approximately 6eV, and the other is -plasmon located at 24.526.5 eV depend-
ing on the structure of different shungite carbons. The plasmon peak of those is
shifted to a lower energy with respect to the peak of graphite and is similar to the
peak of fullerene-like carbon spheres (Kovalevski and Moshnikov, 2001).
Fullerene-Like Carbon in Nature and Perspectives 167
The magnetic susceptibility () is one of the more sensitive physical properties
of the band and atomic structure. For disordered carbon is sensitive to the degree
of graphitization, crystallite size, and the degree of folding of the graphene layers.
The magnetic susceptibilities of shungites from several localities are different at
temperatures ranging from 90 to 150 K. The effect is likely sensitive to the structure
of the graphene layers and the presence of trace elements. A distinctive feature is a
considerable increase of diamagnetism at liquid-nitrogen temperatures with a tem-
perature range and amount of change similar to that of CuC
60
. The effect has not
been reported for amorphous natural carbon and graphite but has been observed for
doped fullerites. The hypothesis that the carbon of shungites is natural fullerene-like
carbon can account for the observed structure and magnetic properties (Kovalevski
et al., 2005).
The features of fullerene-like natural carbon offer the challenge of its use in
science-based technologies. Furthermore, natural fullerene-like carbon from shun-
gite rocks contains trace elements and characterized by a metastable state. The pe-
culiarities can lead to forming at processing of new fullerene-like structures such as
hollow particles and bers and those partially lled by metals or carbide that can be
also used.
Acknowledgements This study was supported by grant 05-05-97520C from RFBR and Republic
of Karelia.
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