Benzene-derived carbon nanothreads

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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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.

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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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Correspondence to John V. Badding.

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The authors declare no competing financial interests.

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Fitzgibbons, T., Guthrie, M., Xu, E. et al. Benzene-derived carbon nanothreads. Nature Mater 14, 43–47 (2015). https://doi.org/10.1038/nmat4088

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