Benzene-derived carbon nanothreads


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.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Figure 1: Bright-field TEM micrographs and X-ray scattering of sp3 nanothreads.
Figure 2: Experimental and modelled PDFs G(r).
Figure 3: Atomistic models and Stone–Wales transformation.
Figure 4: Visible Raman spectra in the C–C mode ‘fingerprint’ region of 12C and 13C nanothreads collected with 633 nm excitation.


  1. 1

    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).

    CAS  Article  Google Scholar 

  2. 2

    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).

    CAS  Article  Google Scholar 

  3. 3

    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).

    CAS  Article  Google Scholar 

  4. 4

    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).

    Article  Google Scholar 

  5. 5

    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).

    CAS  Article  Google Scholar 

  6. 6

    Ciabini, L. et al. Triggering dynamics of the high-pressure benzene amorphization. Nature Mater. 6, 39–43 (2007).

    CAS  Article  Google Scholar 

  7. 7

    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).

    Article  Google Scholar 

  8. 8

    Block, S., Weir, C. E. & Piermarini, G. J. Polymorphism in benzene, naphthalene, and anthracene at high pressure. Science 169, 586–587 (1970).

    CAS  Article  Google Scholar 

  9. 9

    Piermarini, G. J., Mighell, A. D., Weir, C. E. & Block, S. Crystal structure of benzene-2 at 25-kilobars. Science 165, 1250–1255 (1969).

    CAS  Article  Google Scholar 

  10. 10

    Schettino, V. & Bini, R. Constraining molecules at the closest approach: Chemistry at high pressure. Chem. Soc. Rev. 36, 869–880 (2007).

    CAS  Article  Google Scholar 

  11. 11

    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).

    CAS  Article  Google Scholar 

  12. 12

    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).

    CAS  Article  Google Scholar 

  13. 13

    Pruzan, P. et al. Transformation of benzene to a polymer after static pressurization to 30 GPa. J. Chem. Phys. 92, 6910–6915 (1990).

    CAS  Article  Google Scholar 

  14. 14

    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).

    CAS  Article  Google Scholar 

  15. 15

    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).

    Article  Google Scholar 

  16. 16

    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).

    CAS  Article  Google Scholar 

  17. 17

    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).

    CAS  Article  Google Scholar 

  18. 18

    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).

    CAS  Article  Google Scholar 

  19. 19

    Kovacic, P. & Koch, F. W. Polymerization of benzene to p-polyphenyl by ferric chloride. J. Org. Chem. 28, 1864–1867 (1963).

    CAS  Article  Google Scholar 

  20. 20

    Thess, A. et al. Crystalline ropes of metallic carbon nanotubes. Science 273, 483–487 (1996).

    CAS  Article  Google Scholar 

  21. 21

    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).

    Google Scholar 

  22. 22

    Barua, S. R. et al. Polytwistane. Chem. Eur. J. 20, 1638–1645 (2014).

    CAS  Article  Google Scholar 

  23. 23

    Robertson, J. Photoluminescence mechanism in amorphous hydrogenated carbon. Diam. Relat. Mater. 5, 457–460 (1996).

    CAS  Article  Google Scholar 

  24. 24

    Schluter, A. D. Ladder polymers-the new generation. Adv. Mater. 3, 282–291 (1991).

    Article  Google Scholar 

  25. 25

    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).

    CAS  Article  Google Scholar 

  26. 26

    Ciabini, L., Santoro, M., Bini, R. & Schettino, V. High pressure photoinduced ring opening of benzene. Phys. Rev. Lett. 88, 085505 (2002).

    Article  Google Scholar 

  27. 27

    Schettino, V., Bini, R., Ceppatelli, M., Ciabini, L. & Citroni, M. Chemical reactions at very high pressure. Adv. Chem. Phys. 131, 105–242 (2005).

    CAS  Google Scholar 

  28. 28

    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).

    CAS  Article  Google Scholar 

  29. 29

    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).

    CAS  Article  Google Scholar 

Download references


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.

Author information




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.

Corresponding author

Correspondence to John V. Badding.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Information (PDF 2586 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Fitzgibbons, T., Guthrie, M., Xu, E. et al. Benzene-derived carbon nanothreads. Nature Mater 14, 43–47 (2015).

Download citation

Further reading