Abstract
Low-dimensional carbon nanomaterials such as fullerenes, nanotubes, graphene and diamondoids have extraordinary physical and chemical properties1,2. Compression-induced polymerization of aromatic molecules could provide a viable synthetic route to ordered carbon nanomaterials3,4, but despite almost a century of study5,6,7,8,9 this approach has produced only amorphous products10,11,12,13,14. Here we report recovery to ambient pressure of macroscopic quantities of a crystalline one- dimensional sp3 carbon nanomaterial formed by high-pressure solid-state reaction of benzene. X-ray and neutron diffraction, Raman spectroscopy, solid-state NMR, transmission electron microscopy and first-principles calculations reveal close- packed bundles of subnanometre-diameter sp3-bonded carbon threads capped with hydrogen, crystalline in two dimensions and short-range ordered in the third. These nanothreads promise extraordinary properties such as strength and stiffness higher than that of sp2 carbon nanotubes or conven tional high-strength polymers15. They may be the first member of a new class of ordered sp3 nanomaterials synthesized by kinetic control of high-pressure solid-state reactions.
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Dahl, J. E., Liu, S. G. & Carlson, R. M. K. Isolation and structure of higher diamondoids, nanometer-sized diamond molecules. Science 299, 96–99 (2003).
Jariwala, D., Sangwan, V. K., Lauhon, L. J., Marks, T. J. & Hersam, M. C. Carbon nanomaterials for electronics, optoelectronics, photovoltaics, and sensing. Chem. Soc. Rev. 42, 2824–2860 (2013).
Wen, X. D., Hoffmann, R. & Ashcroft, N. W. Benzene under high pressure: A story of molecular crystals transforming to saturated networks, with a possible intermediate metallic phase. J. Am. Chem. Soc. 133, 9023–9035 (2011).
He, C. Y., Sun, L. Z., Zhang, C. X. & Zhong, J. X. Low energy three-dimensional hydrocarbon crystal from cold compression of benzene. J. Phys. Condens. Matter 25, 205403 (2013).
Thiery, M. M. & Leger, J. M. High-pressure solid-phases of benzene. 1. Raman and x-ray studies of C6H6 at 294-K up to 25-GPa. J. Chem. Phys. 89, 4255–4271 (1988).
Ciabini, L. et al. Triggering dynamics of the high-pressure benzene amorphization. Nature Mater. 6, 39–43 (2007).
Bridgman, P. W. Change of phase under pressure. I. The phase diagram of eleven substances with especial reference to the melting curve. Phys. Rev. 3, 153–203 (1914).
Block, S., Weir, C. E. & Piermarini, G. J. Polymorphism in benzene, naphthalene, and anthracene at high pressure. Science 169, 586–587 (1970).
Piermarini, G. J., Mighell, A. D., Weir, C. E. & Block, S. Crystal structure of benzene-2 at 25-kilobars. Science 165, 1250–1255 (1969).
Schettino, V. & Bini, R. Constraining molecules at the closest approach: Chemistry at high pressure. Chem. Soc. Rev. 36, 869–880 (2007).
Ciabini, L., Santoro, M., Bini, R. & Schettino, V. High pressure reactivity of solid benzene probed by infrared spectroscopy. J. Chem. Phys. 116, 2928–2935 (2002).
Citroni, M., Bini, R., Foggi, P. & Schettino, V. Role of excited electronic states in the high-pressure amorphization of benzene. Proc. Natl Acad. Sci. USA 105, 7658–7663 (2008).
Pruzan, P. et al. Transformation of benzene to a polymer after static pressurization to 30 GPa. J. Chem. Phys. 92, 6910–6915 (1990).
Ceppatelli, M., Santoro, M., Bini, R. & Schettino, V. High pressure reactivity of solid furan probed by infrared and Raman spectroscopy. J. Chem. Phys. 118, 1499–1506 (2003).
Stojkovic, D., Zhang, P. H. & Crespi, V. H. Smallest nanotube: Breaking the symmetry of sp3 bonds in tubular geometries. Phys. Rev. Lett. 87, 122502 (2001).
Bini, R., Ceppatelli, M., Citroni, M. & Schettino, V. From simple to complex and backwards. Chemical reactions under very high pressure. Chem. Phys. 398, 262–268 (2012).
Chelazzi, D., Ceppatelli, M., Santoro, M., Bini, R. & Schettino, V. High-pressure synthesis of crystalline polyethylene using optical catalysis. Nature Mater. 3, 470–475 (2004).
Aoki, K., Kakudate, Y., Yoshida, M., Usuba, S. & Fujiwara, S. Solid state polymerization of cyanoacetylene into conjugated linear chains under pressure. J. Chem. Phys. 91, 778–782 (1989).
Kovacic, P. & Koch, F. W. Polymerization of benzene to p-polyphenyl by ferric chloride. J. Org. Chem. 28, 1864–1867 (1963).
Thess, A. et al. Crystalline ropes of metallic carbon nanotubes. Science 273, 483–487 (1996).
Egami, T. & Billinge, S. J. L. Underneath the Bragg Peaks: Structural Analysis of Complex Materials 2nd edn, Vol. 16 (Pergamon Materials Series, Pergamon-Elsevier Science, 2012).
Barua, S. R. et al. Polytwistane. Chem. Eur. J. 20, 1638–1645 (2014).
Robertson, J. Photoluminescence mechanism in amorphous hydrogenated carbon. Diam. Relat. Mater. 5, 457–460 (1996).
Schluter, A. D. Ladder polymers-the new generation. Adv. Mater. 3, 282–291 (1991).
Li, Z. Q., Lu, C. J., Xia, Z. P., Zhou, Y. & Luo, Z. X-ray diffraction patterns of graphite and turbostratic carbon. Carbon 45, 1686–1695 (2007).
Ciabini, L., Santoro, M., Bini, R. & Schettino, V. High pressure photoinduced ring opening of benzene. Phys. Rev. Lett. 88, 085505 (2002).
Schettino, V., Bini, R., Ceppatelli, M., Ciabini, L. & Citroni, M. Chemical reactions at very high pressure. Adv. Chem. Phys. 131, 105–242 (2005).
Klotz, S., Hamel, G. & Frelat, J. A new type of compact large-capacity press for neutron and X-ray scattering. High Press. Res. 24, 219–223 (2004).
Fang, J., Bull, C. L., Loveday, J. S., Nelmes, R. J. & Kamenev, K. V. Strength analysis and optimisation of double-toroidal anvils for high-pressure research. Rev. Sci. Instrum. 83, 093902 (2012).
Acknowledgements
This work was supported as part of the Energy Frontier Research in Extreme Environments (EFree) Center, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science under Award Number DE-SC0001057. Facilities and instrumentation support was provided by the following. X-ray diffraction analyses were performed at the high-pressure collaborative access team (HPCAT) beamline 16 ID-B at the Advanced Photon Source (APS), Argonne National Laboratory (ANL). HPCAT operations are supported by DOE-NNSA under Award No. DE-NA0001974 and DOE-BES under Award No. DE-FG02-99ER45775, with partial instrumentation funding by the National Science Foundation (NSF). X-ray PDF analyses were performed at the X-ray Science Division (XSD) beamline 11 ID-C at the APS. The APS is a US Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by ANL under Contract No. DE-AC02-06CH11357. Sample synthesis was performed at the Spallation Neutrons at Pressure (SNAP) beamline and neutron diffraction analyses were performed at the Nanoscale Ordered Materials Diffractometer (NOMAD) beamline at Oak Ridge National Laboratory’s (ORNL) Spallation Neutron Source (SNS). The work at SNS was sponsored by the Scientific User’s Facility Division, Office of Basic Energy Science, US DOE. SSNMR characterization was performed in part at the SSNMR facility at Arizona State University (ASU). This facility is supported by the ASU Magnetic Resonance Research Center (MRRC). User fees were supported by NSF CHE 1011937. SSNMR measurements were also performed at the W. M. Keck Solid State NMR facility at the Geophysical Laboratory, Carnegie Institution of Washington. J. Neuefeind (ORNL), C. Benmore (ANL), G. Holland (ASU) and J. Yarger (ASU) performed neutron (ORNL), X-ray (ANL) and SSNMR measurements (ASU), respectively. S. Aro (Penn State), K. Li (Carnegie Institution of Washington) and J. Molaison (ORNL) assisted with synthesis. K. Wang and T. Clark of the Penn State Materials Characterization Laboratory (MCL) assisted with TEM measurements. We thank R. Hoffmann, K. Feldman and G. Mahan for valuable discussions.
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T.C.F., M.G. and J.V.B. conceived the project. T.C.F. developed synthesis procedures. T.C.F. and M.G. collected neutron and X-ray diffraction data. T.C.F., M.G., E-s.X., V.H.C. and J.V.B. analysed the diffraction data and PDFs. S.K.D. and G.D.C. collected and analysed SSNMR spectra. T.C.F. collected TEM data under the guidance of N.A. E-s.X. and V.H.C. performed first-principles calculations. T.C.F., M.G., E-s.X., V.H.C. and J.V.B. wrote the manuscript. All authors discussed it.
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Fitzgibbons, T., Guthrie, M., Xu, Es. et al. Benzene-derived carbon nanothreads. Nature Mater 14, 43–47 (2015). https://doi.org/10.1038/nmat4088
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DOI: https://doi.org/10.1038/nmat4088
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