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arbon is the element in the periodic consist of extended networks of sp3- and 1985, with the advent of fullerenes (Fig. 1),
table that provides the basis for life sp2-hybridized carbon atoms, respectively. which were observed for the first time by
on Earth. It is also important for Both forms show unique physical properties Kroto et al.3. This serendipitous discovery
many technological applications, ranging such as hardness, thermal conductivity, marked the beginning of an era of synthetic
from drugs to synthetic materials. This lubrication behaviour or electrical carbon allotropes. Now, as we celebrate
role is a consequence of carbons ability conductivity. Conceptually, many other buckminsterfullerenes 25th birthday, it is
to bind to itself and to nearly all elements ways to construct carbon allotropes are also the time to reflect on a growing family
in almost limitless variety. The resulting possible by altering the periodic binding of synthetic carbon allotropes, which
structural diversity of organic compounds motif in networks consisting of sp3-, sp2- includes the synthesis of carbon nanotubes
and molecules is accompanied by a broad and sp-hybridized carbon atoms1,2. As a in 19914 and the rediscovery of graphene
range of chemical and physical properties. consequence of the expected remarkable in 20045. Keeping in mind the numerous
The tools of modern synthetic chemistry physical properties of these elusive carbon possible carbon modifications and the
allow the tailored design of these properties allotropes, it has been appealing, for number of scientists investigating this
by the controlled combination of structural some time, to develop concepts for their challenge, these revelations have certainly
and functional building blocks in new preparation in macroscopic quantities. not come to an end.
target systems. However, diamond and graphite represented
Elemental carbon exists in two natural the only known allotropes of carbon for synthesis of allotropes
allotropes, diamond and graphite, which a long time. This situation changed in The fullerenes, of which the smallest stable
and most prominent is C60, are molecular
carbon allotropes. C60 consists of a spherical
network of sixty structurally equivalent
sp2-hybridized carbon atoms in the shape
of a football (or, a soccer ball or, more
technically, an Ih-symmetrical truncated
icosahedron) composed of 12 pentagons
Many undiscovered and 20 hexagons. Following the isolation
allotropes for example
sp-sp2-graphyne and structural determination of C60 by
20?? Kroto et al., the first successful preparation
of 0-dimensional fullerenes in macroscopic
Graphene
quantities was reported five years later by
2004
Krtschmer and Huffman6. This involved
the evaporation and recondensation of
graphite using an arc-discharge method to
Carbon nanotubes give C60. Now, fullerenes can be prepared on
1991 the ton scale.
Many representatives of higher
fullerenes7 such as D5h-C70, chiral D2-C76,
Fullerenes D6h-C84 and more recently D5h-C90 (ref. 8)
1985 have been isolated and structurally
characterized. Furthermore, there are several
Figure 1 | The world of synthetic carbon allotropes. In this family, fullerenes represent the most intensively possible ways of derivatizing fullerene
investigated class. Fullerene chemistry is a mature field and many well-defined derivatives with including creating fullerene salts, open-cage
outstanding properties have been synthesized. The first fullerene-based products such as organic solar fullerenes and quasi-fullerenes (Fig. 2).
cells have already entered the market. The materials properties of the carbon nanotubes and especially The latter are spherical, closed structures
those of graphene are considered to be even more promising. However, it is still difficult to control their composed of pentagons and hexagons
chemistry and also the bulk production of uniform monodisperse samples, for example, mass production combined with rings of other sizes. Another
of tubes with single helicities remains a challenge. Graphene chemistry is in its early infancy. Thinking family of fullerenes, namely endohedral
to the future, there are a huge number of elusive carbon allotropes whose predicted properties are fullerenes (Fig. 2f), incorporates guest atoms
unprecedented. Synthetic chemists are developing concepts at present for their preparation and have or molecules inside the carbon framework.
already synthesized partial structures. Examples of endohedral fullerenes include
La@C82 and Sc3N@C80 and, most recently, a Over the past couple of decades,
+
the first endohedral fullerene containing
thousands of well-characterized adducts
an Ih-symmetrical C60 cage, Li@C60, was a+ of C60 and other fullerenes have been
+
structurally characterized9. Exohederal synthesized and show remarkable
+ +
fullerenes those that have been modified
properties. For example, the exohedral
externally are discussed in further + b
R R covalent binding of organic donor
f
detail below. molecules such as porphyrins has attracted
Soon after the discovery of the fullerenes, a lot of attention7, to simulate natural
the formation of quasi-one-dimensional photosynthesis or to transform light
carbon nanotubes out of evaporated graphite into chemical energy. Donoracceptor
was reported4. Later, a series of alternative C60 R R dyads or oligoads such as compound 1
production methods for carbon nanotubes, e c (Fig. 3) undergo photoinduced electron
such as chemical vapour deposition N N R R transfer from the porphyrin donor
methods, were developed10. Depending on to the fullerene acceptor and serve as
the preparation conditions, either single- d ideal model compounds for organic
walled or multiwalled carbon nanotubes solar cells. Indeed, no other compound
are obtained. Carbon nanotubes can be class surpasses fullerenes as electron
considered as seamless, rolled-up graphite acceptors in photovoltaic devices11.
sheets. These tubular networks of bent Adduct 2, namely phenyl-C61-butyric
sp2-hybridized atoms are characterized by a Figure 2 | Possible derivatizations of C60 acid methyl ester (PCBM), serves as an
pronounced one-dimensionality because of (ref. 6): a, fullerene salts; b, exohedral adducts; n-type conductor in very inexpensive
a very high aspect ratio: typical diameters of c, open-cage fullerenes; d, quasi-fullerenes; and comparatively efficient plastic solar
single-walled carbon nanotubes are around e, heterofullerenes; f, endohedral fullerenes. cells11 (bulk heterojunctions) that have
one to two nanometres, but their lengths can already entered the market. Water-soluble
easily reach millimetres and above. Present fullerenes, such as adduct 3 and 4, exhibit
production methods of carbon nanotubes sheer manifold of aesthetically pleasing remarkable biological properties with
lead to the formation of mixtures consisting structures but their outstanding, and often regard to anti-HIV activity 12 and metal-free
of tubes with many different helicities, unprecedented, properties. Common superoxide dismutation, respectively. The
characterized by so-called m,n-values of the to fullerenes, carbon nanotubes and latter is a principal mechanism for efficient
roll-up vectors10. graphene is the presence of fully conjugated neuroprotection13. Further applications
-electrons confined in either zero-, quasi- of fullerene adducts in materials science
Synthetic carbon allotropes one- or two-dimensions. This characteristic include the fields of non-linear optical
conjugation leads to pronounced redox properties14 and liquid crystals15.
represent a growing activity and outstanding electronic Other types of fullerene derivative show
family of fascinating and properties. However, what about the unprecedented properties: for example,
chemical properties of the synthetic carbon salts, such as K3C60 or (TDAE)C60 are
aesthetically pleasing allotropes and their (and derivatives) superconductors16 and ferromagnets17,
architectures with outstanding application as high-performance respectively. Cluster-opened fullerenes
materials? Let us start by taking a look at have been prepared that can be filled with
materials properties. C60: immediately after its availability in small molecules, such as hydrogen, and
macroscopic quantities, it was realized subsequently reclosed to form H2@C60
The youngest synthetic carbon allotrope that chemical functionalization was the (ref. 18). This opens the door to a whole
is two-dimensional graphene, representing key to full exploitation of its vast potential.
a single graphite sheet 5. Graphene, the For example, chemical functionalization a b
ultimate example of expanded aromatic enables a dramatic increase in the solubility N Zn N
carbon, was considered for a very long time of fullerenes, in any solvent, which is N N O
to be an exclusively theoretical material. required for their development as new O O
O
Recently, however, single graphene layers materials or as bioactive redox drugs. O O O O
were prepared successfully by means of a Most importantly, however, chemical O O
simple mechanical exfoliation of graphite functionalization provides the possibility O O
using Scotch tape5. Andre Geim and of combining the unique properties of
Konstantin Novoselov, who headed the fullerenes with those of other compounds.
team behind the discovery of the exfoliation Exohedral addition reactions to the c d HO
O
method and an associated investigation of conjugated -system represent the most R R OHO OHO
the electronic properties of graphene, were important functionalization methods O
O O
O
awarded the 2010 Nobel Prize in Physics. realized so far 7 (Fig. 2b). The driving force O O O O
Of the three families of carbon allotropes, for exohedral additions is the reduction O O
O O
graphene is the most structurally uniform of strain energy stored in the spherical
material where only the sheet extensions and carbon framework. Additions usually
nature of edges can differ. occur regioselectively at fusions of two
six-membered rings, because in contrast R = (CH2)2NHC(O)(CH2)2COOH
Properties of fullerenes to the neighbouring [5,6]-bonds, these
What makes synthetic carbon allotropes [6,6]-bonds are shorter and have more Figure 3 | Some examples of fullerene derivatives
so attractive for scientists is not only the double-bond character. with outstanding materials or biological properties.
Andreas Hirsch is in the Department of Chemistry 3. Kroto, H. W. et al. Nature 318, 162163 (1985). 15. Campidelli, S. et al. Chem. Commun. 42824284 (2006).
and Pharmacy & Interdisciplinary Center of 4. Iijima, S. Nature 354, 5658 (1991). 16. Holczer, K. et al. Science 252, 11541157 (1991).
5. Novoselov, K. & Geim, A. et al. Science 306, 666669 (2004). 17. Allemand, P. M. et al. Science 253, 301302 (1991).
Molecular Materials (ICMM), Friedrich-Alexander- 6. Krtschmer, W. et al. Nature 347, 354358 (1990). 18. Komatsu, K. et al. Science 307, 238240 (2005).
University Erlangen-Nuremberg, Henkestrasse 42, 7. Hirsch, A. & Brettreich, M. Fullerenes Chemistry and Reactions 19. Vostrowsky, O. & Hirsch, A. Chem. Rev. 106, 51915207 (2006).
91054 Erlangen, Germany. (Wiley, 2004). 20. Siegle, V. et al. Nano Lett. doi:10.1021/nl101023u (2010).
e-mail: andreas.hirsch@chemie.uni-erlangen.de 8. Yang, H. et al. Angew. Chem. Int. Ed. 49, 886 (2010). 21. Shim, B. S. et al. Nano Lett. 8, 41514157 (2008).
9. Aoyagi, S. et al. Nature Chem. 2, 678683 (2010). 22. Bae, S. et al. Nature Nanotech. 5, 574578 (2010).
10. Hirsch, A. & Vostrowsky, O. Top. Curr. Chem. 23. Diederich, F. & Kivala, M. Adv. Mat. 22, 803812 (2010).
References 245, 193237 (2005).
1. Karfunkel, H. R. & Dressler, T. J. Am. Chem. Soc. 11. Dennler, G. et al. Adv. Mater. 21, 13231338 (2009).
114, 22852288 (1992). 12. Friedman, S. H. et al. J. Am. Chem. Soc. 115 65066509 (1993). Acknowledgements
2. Diederich, F. & Rubin, Y. Angew. Chem. Int. Ed. 13. Liu, G-F. et al. Angew. Chem. Int. Ed. 47, 39913994 (2008). A.H. thanks GRAPENOCHEM and the Cluster of
31, 11011123 (1992). 14. Koudoumas, E. et al. Chem. Eur. J. 9, 1529 (2003). Excellence EAM for financial support.
C
arbon-based resources (coal, natural and even in the next 5 to 10 years is still The concept of a bridge to a renewable
gas and oil) give us most of the worlds extremely limited when put into the energy future is not new, and many strategies
energy today, but the energy economy context of total world use of fossil fuels. have been offered as near-term alternatives
of the future must necessarily be far more For example, the world used the equivalent to conventional carbon resources3. Although
diverse. Energy generation through solar, of 113,900 terawatts hours [TWh] of fossil some of these concepts appear at first glance
wind and geothermal means is developing energy to fuel economic activity, human to be green solutions, further scrutiny
now, but not fast enough to meet our mobility, and global telecommunications, that takes into account the energy lifecycle
expanding global energy needs. We advocate among other modern day activities in and environmental consequences suggests
that green carbon, which enables us to use 2007. Replacing those terawatts hours with a more murky set of trade-offs. Biodiesel,
carbon-based sources with high efficiency non-fossil energy would be the equivalent of for example, has led to destruction of vast
and in an environmentally friendly manner, constructing an extra 6,020 nuclear plants areas of tropical rainforest to make palm
will provide our society time to develop across the globe or 14 times the number of oil4. A shift of transportation to lithium
alternative energy technologies and markets nuclear power plants in the world today. battery-powered cars requires enormous
without sacrificing environmental or In renewable energy terms, it is 133 times amounts of fossil fuels to mine vast stretches
economic quality. Green carbon will help the amount of solar, wind and geothermal of the Earth in search of lithium, and
to reduce the loss of our precious carbon energy currently in use on the planet.1 the vehicle would need to be driven tens
resources, which are better reserved for Barring a huge reduction in our global of thousands of kilometres entirely on
high-value chemicals, and it will ensure standard of living, we will need to rely renewable energy just to accrue back the
that those hydrocarbons used for fuels on carbon-based energy for some time. ~1.7 GJ energy per kilowatt hour capacity
will minimize carbon emissions. Through Whether this will last for several decades or used for the lithium mining and battery
intensive research and development in into the next century is unclear, but what manufacture5. The electric grid promised
green carbon, our society can guarantee an is apparent is that renewable approaches to serve the purportedly clean electric-car
energy future that uses carbon strategically, to energy generation are increasing at an technology may just become a long tailpipe
without smokestacks, greenhouse gases and annual rate of 7.2% compared with 1.6% for connecting the plug-in batteries to coal-
extensive environmental damage. non-renewable growth2, and the continued fired power plants6. And even if renewable
growth of renewables will demand sustained energies could supply the electricity, the
Building a solid bridge government support. During this transition current electrical grids could not sustain
There is a chasm between the diminutive we propose a green carbon bridge that the vast increase in demand. We need to
proportions of renewable energy currently minimizes the environmental impact of quantify the full environmental or lifecycle
available and our overwhelming dependence carbon fuels and lowers our reliance on these consequences of various options for our
on fossil fuels that currently propel society. resources for primary energy generation. energy bridge if we are to build it from the
The energy policy review of the Obama Ultimately, green carbon will use hydrogen proper technologies.
administration makes this soberingly from renewable sources, while at the same We must also consider energy
clear: The use of renewable energy today time producing basic chemical feedstocks. technology options in a broader context. In