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Title: Coherent coexistence of nanodiamonds and carbon onions in icosahedral core-shell particles

Abstract

In icosahedral carbon nanoparticles, the diamond-like core can undergo a reversible topological transition into and coexist coherently with the onion shells. The general approach for describing and designing complex hierarchical icosahedral structures is discussed. Structural models of icosahedral carbon nanoparticles in which the local arrangement of atoms is virtually identical to that in diamond are derived. It is shown that icosahedral diamond-like particles can be transformed into onion-like shell structures (and vice versa) by the consecutive smoothing (puckering) of atomic networks without disturbance of their topological integrity. The possibility of coherent coexistence of icosahedral diamond-like core with onion shells is shown.

Authors:
;  [1];  [2];  [3]
  1. Grebenshchikov Institute of Silicate Chemistry, Russian Academy of Sciences, nab. Makarova 2, Saint Petersburg 199034 (Russian Federation)
  2. School of Crystallography, Birkbeck College, University of London, Malet Street, London WC1E 7HX (United Kingdom)
  3. (Russian Federation)
Publication Date:
OSTI Identifier:
22347665
Resource Type:
Journal Article
Resource Relation:
Journal Name: Acta Crystallographica. Section A, Foundations of Crystallography; Journal Volume: 63; Journal Issue: Pt 2; Other Information: PMCID: PMC2525862; PUBLISHER-ID: dm5003; PMID: 17301478; OAI: oai:pubmedcentral.nih.gov:2525862; Copyright (c) International Union of Crystallography 2007; This is an open-access article distributed under the terms described at http://journals.iucr.org/services/termsofuse.html.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
Denmark
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; ATOMS; DIAMONDS; DISTURBANCES; NANOPARTICLES; SHELLS; STRUCTURAL MODELS

Citation Formats

Shevchenko, Vladimir Ya., E-mail: shevchenko@isc.nw.ru, Madison, Alexey E., Mackay, Alan L., and Grebenshchikov Institute of Silicate Chemistry, Russian Academy of Sciences, nab. Makarova 2, Saint Petersburg 199034. Coherent coexistence of nanodiamonds and carbon onions in icosahedral core-shell particles. Denmark: N. p., 2007. Web. doi:10.1107/S0108767307002723.
Shevchenko, Vladimir Ya., E-mail: shevchenko@isc.nw.ru, Madison, Alexey E., Mackay, Alan L., & Grebenshchikov Institute of Silicate Chemistry, Russian Academy of Sciences, nab. Makarova 2, Saint Petersburg 199034. Coherent coexistence of nanodiamonds and carbon onions in icosahedral core-shell particles. Denmark. doi:10.1107/S0108767307002723.
Shevchenko, Vladimir Ya., E-mail: shevchenko@isc.nw.ru, Madison, Alexey E., Mackay, Alan L., and Grebenshchikov Institute of Silicate Chemistry, Russian Academy of Sciences, nab. Makarova 2, Saint Petersburg 199034. Thu . "Coherent coexistence of nanodiamonds and carbon onions in icosahedral core-shell particles". Denmark. doi:10.1107/S0108767307002723.
@article{osti_22347665,
title = {Coherent coexistence of nanodiamonds and carbon onions in icosahedral core-shell particles},
author = {Shevchenko, Vladimir Ya., E-mail: shevchenko@isc.nw.ru and Madison, Alexey E. and Mackay, Alan L. and Grebenshchikov Institute of Silicate Chemistry, Russian Academy of Sciences, nab. Makarova 2, Saint Petersburg 199034},
abstractNote = {In icosahedral carbon nanoparticles, the diamond-like core can undergo a reversible topological transition into and coexist coherently with the onion shells. The general approach for describing and designing complex hierarchical icosahedral structures is discussed. Structural models of icosahedral carbon nanoparticles in which the local arrangement of atoms is virtually identical to that in diamond are derived. It is shown that icosahedral diamond-like particles can be transformed into onion-like shell structures (and vice versa) by the consecutive smoothing (puckering) of atomic networks without disturbance of their topological integrity. The possibility of coherent coexistence of icosahedral diamond-like core with onion shells is shown.},
doi = {10.1107/S0108767307002723},
journal = {Acta Crystallographica. Section A, Foundations of Crystallography},
number = Pt 2,
volume = 63,
place = {Denmark},
year = {Thu Mar 01 00:00:00 EST 2007},
month = {Thu Mar 01 00:00:00 EST 2007}
}
  • We describe the topology, structure, and stability of giant fullerenes exhibiting various symmetries (I, Ih, D2h, T). Our results demonstrate that it is also possible to create two new families of nested-chiral-icosahedral (I) fullerenes namely C260@ C560@ C980@ C1520@..and C140@ C380@ C740@ C1220@..., which exhibit interlayer separations of ca. 3.4. These chiral fullerenes are thought to possess non semiconducting properties. Finally, we study in detail the transformation of polyhedral graphitic particles into quasi-spherical nested giant fullerenes by reorganization of carbon atoms which result in the formation of additional pentagonal and heptagonal carbon rings. These spherical structures are metastable and wemore » believe they could be formed if conditions during formation are extreme such as high energy electron irradiation. There is circumstantial experimental evidence for the presence of heptagonal rings within these spherical fullerenes.« less
  • We simulate the experimentally observed graphitization of nanodiamonds into multi-shell onion-like carbon nanostructures, also called carbon onions, at different temperatures, using reactive force fields. The simulations include long-range Coulomb and van der Waals interactions. Our results suggest that long-range interactions play a crucial role in the phase-stability and the graphitization process. Graphitization is both enthalpically and entropically driven and can hence be controlled with temperature. The outer layers of the nanodiamond have a lower kinetic barrier toward graphitization irrespective of the size of the nanodiamond and graphitize within a few-hundred picoseconds, with a large volume increase. The inner core ofmore » the nanodiamonds displays a large size-dependent kinetic barrier, and graphitizes much more slowly with abrupt jumps in the internal energy. It eventually graphitizes by releasing pressure and expands once the outer shells have graphitized. The degree of transformation at a particular temperature is thereby determined by a delicate balance between the thermal energy, long-range interactions, and the entropic/enthalpic free energy gained by graphitization. Upon full graphitization, a multi-shell carbon nanostructure appears, with a shell-shell spacing of about {approx}3.4 {angstrom} for all sizes. The shells are highly defective with predominantly five- and seven-membered rings to curve space. Larger nanodiamonds with a diameter of 4 nm can graphitize into spiral structures with a large ({approx}29-atom carbon ring) pore opening on the outermost shell. Such a large one-way channel is most attractive for a controlled insertion of molecules/ions such as Li ions, water, or ionic liquids, for increased electrochemical capacitor or battery electrode applications.« less
  • We simulate the experimentally observed graphitization of nanodiamonds into multi-shell onion-like carbon nanostructures, also called carbon onions, at different temperatures, using reactive force fields. The simulations include long-range Coulomb and van der Waals interactions. Our results suggest that long-range interactions play a crucial role in the phase-stability and the graphitization process. Graphitization is both enthalpically and entropically driven and can hence be controlled with temperature. The outer layers of the nanodiamond have a lower kinetic barrier toward graphitization irrespective of the size of the nanodiamond and graphitize within a few-hundred picoseconds, with a large volume increase. The inner core ofmore » the nanodiamonds displays a large size-dependent kinetic barrier, and graphitizes much more slowly with abrupt jumps in the internal energy. It eventually graphitizes by releasing pressure and expands once the outer shells have graphitized. The degree of transformation at a particular temperature is thereby determined by a delicate balance between the thermal energy, long-range interactions, and the entropic/enthalpic free energy gained by graphitization. Upon full graphitization, a multi-shell carbon nanostructure appears, with a shell-shell spacing of about {approx}3.4 {angstrom} for all sizes. The shells are highly defective with predominantly five- and seven-membered rings to curve space. Larger nanodiamonds with a diameter of 4 nm can graphitize into spiral structures with a large ({approx}29-atom carbon ring) pore opening on the outermost shell. Such a large one-way channel is most attractive for a controlled insertion of molecules/ions such as Li ions, water, or ionic liquids, for increased electrochemical capacitor or battery electrode applications.« less
  • We simulate the experimentally observed graphitization of nanodiamonds into multi-shell onion-like carbonnanostructures, also called carbon onions, at different temperatures, using reactive force fields. The simulations include long-range Coulomb and van der Waals interactions. Our results suggest that long-range interactions play a crucial role in the phase-stability and the graphitization process. Graphitization is both enthalpically and entropically driven and can hence be controlled with temperature. The outer layers of the nanodiamond have a lower kinetic barrier toward graphitization irrespective of the size of the nanodiamond and graphitize within a few-hundred picoseconds, with a large volume increase. The inner core of themore » nanodiamonds displays a large size-dependent kinetic barrier, and graphitizes much more slowly with abrupt jumps in the internal energy. It eventually graphitizes by releasing pressure and expands once the outer shells have graphitized. The degree of transformation at a particular temperature is thereby determined by a delicate balance between the thermal energy, long-range interactions, and the entropic/enthalpic free energy gained by graphitization. Upon full graphitization, a multi-shell carbonnanostructure appears, with a shell-shell spacing of about ~3.4 Å for all sizes. The shells are highly defective with predominantly five- and seven-membered rings to curve space. Larger nanodiamonds with a diameter of 4 nm can graphitize into spiral structures with a large (~29-atom carbon ring) pore opening on the outermost shell. Such a large one-way channel is most attractive for a controlled insertion of molecules/ions such as Li ions, water, or ionic liquids, for increased electrochemical capacitor or battery electrode applications.« less