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fullerene
chemical compound

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Written by David R.M. Walton , Harold W. Kroto See All

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Fullerene, any of a series of hollow

carbon molecules that form either a
closed cage (“buckyballs”) or a cylinder
(carbon “nanotubes”). The first fullerene
was discovered in 1985 by Sir Harold W.
zoom_in
Kroto (one of the authors of this article)
of the United Kingdom and by Richard E.
Smalley and Robert F. Curl, Jr., of the fullerene

United States. Using a laser to vaporize

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graphite rods in an atmosphere of helium
gas, these chemists and their assistants Category: Science & Tech
obtained cagelike molecules composed of Also called: buckminsterfullerene
60 carbon atoms (C60) joined together by Key People: Richard E. Smalley •
single and double bonds to form a hollow Sir Harold W. Kroto • Robert Curl

sphere with 12 pentagonal and 20 Related Topics: cluster • carbon •

carbon nanotube • fulleride • C60
hexagonal faces—a design that resembles
a football, or soccer ball. In 1996 the trio See all related content →
was awarded the Nobel Prize for their
pioneering efforts. The C60 molecule was
named buckminsterfullerene (or, more simply, the buckyball) after the
American architect R. Buckminster Fuller, whose geodesic dome is
constructed on the same structural principles. The elongated cousins of
buckyballs, carbon nanotubes, were identified in 1991 by Iijima Sumio of
Japan.

The fullerenes, particularly the highly symmetrical C60 sphere, have a

beauty and elegance that excites the imagination of scientists and
nonscientists alike, as they bridge aesthetic gaps between the sciences,
architecture, mathematics, engineering, and the visual arts. Prior to their
discovery, only two well-defined allotropes of carbon were known—
diamond (composed of a three-dimensional crystalline array of carbon
atoms) and graphite (composed of stacked sheets of two-dimensional
hexagonal arrays of carbon atoms). The fullerenes constitute a third form,
and it is remarkable that their existence evaded discovery until almost the
end of the 20th century. Their discovery has led to an entirely new
understanding of the behaviour of sheet materials, and it has opened an
entirely new chapter of nanoscience and nanotechnology—the “new
chemistry” of complex systems at the atomic scale that exhibit advanced
materials behaviour. Nanotubes in particular exhibit a wide range of novel
mechanical and electronic properties. They are excellent conductors of heat
and electricity, and they possess an astonishing tensile strength. Such
properties hold the promise of exciting applications in electronics, structural
materials, and medicine. Practical applications, however, will only be
realized when accurate structural control has been achieved over the
synthesis of these new materials.

Buckminsterfullerenes
During the period 1985–90 Kroto, working with colleagues at the University
of Sussex, Brighton, England, used laboratory microwave spectroscopy
techniques to analyze the spectra of carbon chains. These measurements
later led to the detection, by radioastronomy, of chainlike molecules
consisting of 5 to 11 carbon atoms in interstellar gas clouds and in the
atmospheres of carbon-rich red giant stars. On a visit to Rice University,
Houston, Texas, in 1984, Curl, an authority on microwave and infrared
spectroscopy, suggested that Kroto see an ingenious laser–supersonic cluster
beam apparatus developed by Smalley. The apparatus could vaporize any
material into a plasma of atoms and then be used to study the resulting
clusters (aggregates of tens to many tens of atoms). During the visit, Kroto
realized that the technique might be used to simulate the chemical
conditions in the atmosphere of carbon stars and so provide compelling
evidence for his conjecture that the chains originated in stars. In a now-
famous 11-day series of experiments conducted in September 1985 at Rice
University by Kroto, Smalley, and Curl and their student coworkers James
Heath, Yuan Liu, and Sean O’Brien, Smalley’s apparatus was used to
simulate the chemistry in the atmosphere of giant stars by turning the
vaporization laser onto graphite. The study not only confirmed that carbon
chains were produced but also showed, serendipitously, that a hitherto
unknown carbon species containing 60 atoms formed spontaneously in
relatively high abundance. Attempts to explain the remarkable stability of
the C60 cluster led the scientists to the conclusion that the cluster must be a
spheroidal closed cage in the form of a truncated icosahedron—a polygon
with 60 vertices and 32 faces, 12 of which are pentagons and 20 hexagons.
They chose the imaginative name buckminsterfullerene for the cluster in
honour of the designer-inventor of the geodesic domes whose ideas had
influenced their structure conjecture.

From 1985 to 1990, a series of studies indicated that C60, and also C70, were
indeed exceptionally stable and provided convincing evidence for the cage
structure proposal. In addition, evidence was obtained for the existence of
other smaller metastable species, such as C28, C36, and C50, and experimental
evidence was provided for “endohedral” complexes, in which an atom was
trapped inside the cage. Experiments showed that the size of an
encapsulated atom determined the size of the smallest surrounding possible
cage. In 1990 physicists Donald R. Huffman of the United States and
Wolfgang Krätschmer of Germany announced a simple technique for
producing macroscopic quantities of fullerenes, using an electric arc
between two graphite rods in a helium atmosphere to vaporize carbon. The
resulting condensed vapours, when dissolved in organic solvents, yielded
crystals of C60. With fullerenes now available in workable amounts, research
on these species expanded to a remarkable degree, and the field of fullerene
chemistry was born.
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The C60 molecule undergoes a wide range of novel chemical reactions. It

readily accepts and donates electrons, a behaviour that suggests possible
applications in batteries and advanced electronic devices. The molecule
readily adds atoms of hydrogen and of the halogen elements. The halogen
atoms can be replaced by other groups, such as phenyl (a ring-shaped
hydrocarbon with the formula C6H5 that is derived from benzene), thus
opening useful routes to a wide range of novel fullerene derivatives. Some of
these derivatives exhibit advanced materials behaviour. Particularly
important are crystalline compounds of C60 with alkali metals and alkaline
earth metals; these compounds are the only molecular systems to exhibit
superconductivity at relatively high temperatures above 19 K.
Superconductivity is observed in the range 19 to 40 K, equivalent to −254 to
−233 °C or −425 to −387 °F.

Particularly interesting in fullerene chemistry are the so-called endohedral

species, in which a metal atom (given the generic designation M) is
physically trapped inside a fullerene cage. The resulting compounds
(assigned the formulas M@C60) have been extensively studied. Alkali metals
and alkaline earth metals as well as early lanthanoids may be trapped by
vaporizing graphite disks or rods impregnated with the selected metal.
Helium (He) can also be trapped by heating C60 in helium vapour under
pressure. Minute samples of He@C60 with unusual isotope ratios have been
found at some geologic sites, and samples also found in meteorites may yield
information on the origin of the bodies in which they were found.

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Carbon nanotubes
In 1991 Iijima Sumio of NEC Corporation’s Fundamental Research
Laboratory, Tsukuba Science City, Japan, investigated material extracted
from solids that grew on the tips of carbon electrodes after being discharged
under C60 formation conditions. Iijima found that the solids consisted of tiny
tubes made up of numerous concentric “graphene” cylinders, each cylinder
wall consisting of a sheet of carbon atoms arranged in hexagonal rings. The
cylinders usually had closed-off ends and ranged from 2 to 10 micrometres
(millionths of a metre) in length and 5 to 40 nanometres (billionths of a
metre) in diameter. High-resolution transmission electron microscopy later
revealed that these multiwalled carbon nanotubes (MWNTs) are seamless
and that the spacings between adjacent layers is about 0.34 nanometre, close
to the spacing observed between sheets of graphite. The number of
concentric cylinders in a given tube ranged from 3 to 50, and the ends were
generally capped by fullerene domes that included pentagonal rings
(necessary for closure of the tubes). It was soon shown that single-walled
nanotubes (SWNTs) could be produced by this method if a cobalt-nickel
catalyst was used. In 1996 a group led by Smalley produced SWNTs in high
purity by laser vaporization of carbon impregnated with cobalt and nickel.
These nanotubes are essentially elongated fullerenes.

Individual carbon nanotubes may be metallic or semiconducting, depending

on the helical orientation of the rows of hexagonal rings in the walls of the
tubes. Rather than conducting electricity via electron transport, a diffusive
process that results in electron scattering and conductive heating, SWNTs
exhibit ballistic transport, a highly efficient and fast conduction process in
which electrons, prevented from diffusing through the wall of the tube or
around its circumference by the regular hexagonal array of carbon atoms,
propagate rapidly along the axis of the tube. Open-ended SWNTs emit
electrons at currents that attain approximately 100 nanoamperes (billionths
of an ampere). Owing to such remarkable properties, electrical conductors
made of bundles of nanotubes should exhibit zero energy loss. Aligned
MWNTs show promise as field-emission devices with potential applications
in electronic flat-panel displays. Nanotubes may also be used as highly
resilient probe tips for scanning tunneling microscopes and atomic force
microscopes.

Carbon nanotubes exhibit faster phonon transport than diamond, which

was previously recognized as the best thermal conductor, and the electric
current-carrying capacity of nanotubes is approximately four orders of
magnitude higher than that of copper. The Young’s modulus of MWNTs (a
measure of their elasticity, or ability to recover from stretching or
compression) is estimated by researchers to be greater than that of carbon
fibres by a factor of 5 to 10. MWNTs are capable of readily absorbing loads
via a sequence of reversible elastic deformations, such as buckling or
kinking, in which the bonds between carbon atoms remain intact.

Nanotubes can be “decapped” by oxidation and the resulting opened tubes

filled with metals, such as lead, or even with buckyballs. Boron and nitrogen
atoms may be incorporated into carbon nanotube walls. Microscopic metal
particles that would otherwise be rapidly oxidized may be stabilized in air
by encapsulation in nanotube skins.

Potential applications of fullerenes

The discovery of C60 has led to a paradigm shift in the understanding of
graphite, in particular graphene sheets on a small scale. It is now known
that the most stable form of a carbon aggregate, containing tens to several
thousands of atoms, is a closed buckyball or nanotube. This new
understanding is not restricted to pure carbon but also applies to other
sheet-forming materials such as boron nitride, which can also form
nanotubes. Closed fullerene structures, incorporating sulfides of such metals
as tungsten and molybdenum, exhibit excellent solid-lubricant properties.
Conducting carbon nanotubes may be coated with sheaths of metal sulfides
to produce tiny insulated electrical wire.

Fullerenes and nanotubes have engendered much excitement, especially

with regard to possible future applications, but so far such applications have
been few and far between. Nanotubes in particular may well bring about a
revolution in materials science. For example, if SWNTs can be made in
bundles of 100 billion, then a material will be produced that may approach
the limits of tensile strength possible for any known material involving the
chemical bond. In practice, no material approaches its theoretical “intrinsic
strength,” because of breakdowns brought on by the propagation of
microscopic defects through the material. A bundle of nanotubes, however,
may bypass this problem, as microscopic defects may anneal along the
length of a particular tube and certainly should not propagate across the
bundle—thus avoiding the problems that occur in conventional materials.
Estimates of potential tensile strength vary, but it is predicted that a 1-metre
rod may reach 50 to 100 times the strength of steel at one-sixth the weight.
The impact of such a material on civil engineering, building construction,
aircraft, and automobiles would be spectacular. In order to realize this
potential, however, new processes will have to be discovered that can
produce long (more than 1 metre), perfectly ordered bundles in which all
100 billion nanotubes preferably have the same diameter and atomic
arrangement. At present the technology to achieve this does not exist;
indeed, it is not even obvious what strategy might be used to reach this goal.
More realistically, carbon-nanotube composite materials exhibiting
improved behaviour over standard carbon-fibre composites are likely in the
near term. In addition, applications on a small scale should be feasible for
medical purposes—for instance, the strength of individual nanotubes may
prove useful in microsurgery or nanosurgery.

Harold W. Kroto

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