Abstract
Graphite vaporization provides an uncontrolled yet efficient means of producing fullerene molecules. However, some fullerene derivatives or unusual fullerene species might only be accessible through rational and controlled synthesis methods. Recently, such an approach has been used1 to produce isolable amounts of the fullerene C60 from commercially available starting materials. But the overall process required 11 steps to generate a suitable polycyclic aromatic precursor molecule, which was then dehydrogenated in the gas phase with a yield of only about one per cent. Here we report the formation of C60 and the triazafullerene C57N3 from aromatic precursors using a highly efficient surface-catalysed cyclodehydrogenation process. We find that after deposition onto a platinum (111) surface and heating to 750 K, the precursors are transformed into the corresponding fullerene and triazafullerene molecules with about 100 per cent yield. We expect that this approach will allow the production of a range of other fullerenes and heterofullerenes2,3, once suitable precursors are available. Also, if the process is carried out in an atmosphere containing guest species, it might even allow the encapsulation of atoms or small molecules to form endohedral fullerenes4,5.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 51 print issues and online access
$199.00 per year
only $3.90 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Scott, L. T. et al. A rational chemical synthesis of C60 . Science 295, 1500–1503 (2002)
Hummelen, J. C., Knight, B., Pavlovich, J., González, R. & Wudl, F. Isolation of the heterofullerene C59N as its dimer (C59N)2 . Science 269, 1554–1556 (1995)
Vostrowsky, O. & Hirsch, A. Heterofullerenes. Chem. Rev. 106, 5191–5207 (2006)
Komatsu, K., Murata, M. & Murata, Y. Encapsulation of molecular hydrogen in fullerene C60 by organic synthesis. Science 307, 238–240 (2005)
Iwamatsu, S.-I. et al. Carbon monoxide inside an open-cage fullerene. Angew. Chem. Int. Ed. 45, 5337–5340 (2006)
Gómez-Lor, B., de Frutos, Ó. & Echavarren, A. M. Synthesis of ‘crushed fullerene’ C60H30 . Chem. Commun. 2431–2432 (1999)
Gómez-Lor, B. et al. Zipping up ‘the crushed fullerene’ C60H30: C60 by fifteen-fold, consecutive intramolecular H2 losses. Chem. Commun. 370–371 (2002)
Gómez-Lor, B. & Echavarren, A. M. Synthesis of a triaza analogue of crushed-fullerene by intramolecular palladium catalysed arylation. Org. Lett. 6, 2993–2996 (2004)
Jelinek, P., Wang, H., Lewis, J. P., Sankey, O. F. & Ortega, J. Multicenter approach to the exchange-correlation interactions in ab initio tight-binding methods. Phys. Rev. B 71, 235101 (2005)
Segall, M. D. et al. First-principles simulation: ideas, illustrations and the CASTEP code. J. Phys. Condens. Matter 14, 2717–2744 (2002)
Orzali, T., Petukhov, M., Sambi, M. & Tondello, E. STM study of the initial stages of C60 adsorption on the Pt(110)-(1×2) surface. Appl. Surf. Sci. 252, 5534–5537 (2006)
Weckesser, J., Barth, J. V. & Kern, K. Mobility and bonding transition of C60 on Pd(110). Phys. Rev. B 64, 161403 (2001)
Felici, R. et al. X-ray-diffraction characterization of Pt(111) surface nanopatterning induced by C60 adsorption. Nature Mater. 4, 688–692 (2005)
Orzali, T. et al. Temperature-dependent self-assemblies of C60 on (1 × 2)-Pt(110): A STM/DFT investigation. J. Phys. Chem. C 112, 378–390 (2008)
Pascual, J. I. et al. Seeing molecular orbitals. Chem. Phys. Lett. 321, 78–82 (2000)
Schull, G. & Berndt, R. Orientationally ordered (7 × 7) superstructure of C60 on Au(111). Phys. Rev. Lett. 99, 226105 (2007)
Hellgren, N. et al. Electronic structure of carbon nitride thin films studied by X-ray spectroscopy techniques. Thin Solid Films 471, 19–34 (2005)
Soto, G. Synthesis of PtN x films by reactive laser ablation. Mater. Lett. 58, 2178–2180 (2004)
Lesnard, H., Bocquet, M. L. & Lorente, N. Dehydrogenation of aromatic molecules under a scanning tunnelling microscope: Pathways and inelastic spectroscopy simulations. J. Am. Chem. Soc. 129, 4298–4305 (2007)
Rubin, Y. Ring opening reactions of fullerenes: Designed approaches to endohedral metal complexes. Top. Curr. Chem. 199, 67–91 (1999)
Murata, Y., Murata, M. & Komatsu, K. Synthesis, structure, and properties of novel open-cage fullerenes having heteroatom(s) on the rim of the orifice. Chem. Eur. J. 9, 1600–1609 (2003)
Gale, R. J., Salmeron, M. & Somorjai, G. A. Variation of surface-reaction probability with reactant angle of incidence – molecular-beam study of asymmetry of stepped platinum crystal-surfaces for H-H bond breaking. Phys. Rev. Lett. 38, 1027–1029 (1977)
Acknowledgements
Authors acknowledge financial support from the national Spanish funding agency DGICYT-MEC (programmes MAT, CONSOLIDER and CTQ) and the ICIQ Foundation. Computer time was provided by the Spanish National Supercomputing Network at the MareNostrun (BSC) and Magerit (CESVIMA) supercomputers.
Author Contributions G.O. performed the experimental work related to the UHV system. G.B. performed the ab initio calculations. C.S.-S., R.C., M.F.L., C.R., F.J.P. and J.M. helped with STM-STS, TDS and XPS experiments and preliminary synchrotron radiation measurements. A.M.E and B.G.-L. designed and synthesized the planar precursors of (hetero)fullerenes. N.C. performed the mass spectrometry experiments. M.A.B. and J.O. wrote part of the calculation code and input and made preliminary calculations. The work was coordinated by B.G.-L. (chemistry), R.P. (theory) and J.A.M.-G. (experiment: UHV-STM molecular deposition, characterization and cyclization).
Author information
Authors and Affiliations
Corresponding authors
Supplementary information
Supplementary information
The file contains Supplementary Methods, Supplementary Discussion, Supplementary Figures S1-S7 with Legends and additional references. (PDF 1563 kb)
Rights and permissions
About this article
Cite this article
Otero, G., Biddau, G., Sánchez-Sánchez, C. et al. Fullerenes from aromatic precursors by surface-catalysed cyclodehydrogenation. Nature 454, 865–868 (2008). https://doi.org/10.1038/nature07193
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1038/nature07193
This article is cited by
-
Upcycling process of transforming waste coffee into spherical graphene by flash pyrolysis for sustainable supercapacitor manufacturing with virgin graphene electrodes and its comparative life cycle assessment
Biomass Conversion and Biorefinery (2024)
-
Gas phase synthesis of the C40 nano bowl C40H10
Nature Communications (2023)
-
Fully conjugated azacorannulene dimer as large diaza[80]fullerene fragment
Nature Communications (2022)
-
DFT investigation on electrophilic and nucleophilic activities of some nitrogen-doped fullerenes, in comparison to C60
Structural Chemistry (2020)
-
Selective on-surface covalent coupling based on metal-organic coordination template
Nature Communications (2019)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.
