Atomic-scale time-resolved imaging of krypton dimers, chains and transition to a one-dimensional gas
Atomic-scale time-resolved imaging of krypton dimers, chains and transition to a one-dimensional gas
Single-atom dynamics of noble-gas elements have been investigated using time-resolved transmission electron microscopy (TEM), with direct observation providing for a deeper understanding of chemical bonding, reactivity, and states of matter at the nanoscale. We report on a nanoscale system consisting of endohedral fullerenes encapsulated within single-walled carbon nanotubes ((Kr@C60)@SWCNT), capable of the delivery and release of krypton atoms on-demand, via coalescence of host fullerene cages under the action of the electron beam (in situ) or heat (ex situ). The state and dynamics of Kr atoms were investigated by energy dispersive X-ray spectroscopy (EDS), electron energy loss spectroscopy (EELS), and X-ray photoelectron spectroscopy (XPS). Kr atom positions were measured precisely using aberration-corrected high-resolution TEM (AC-HRTEM), aberration-corrected scanning TEM (AC-STEM), and single-atom spectroscopic imaging (STEM-EELS). The electron beam drove the formation of 2Kr@C120 capsules, in which van der Waals Kr2 and transient covalent [Kr2]+ bonding states were identified. Thermal coalescence led to the formation of longer coalesced nested nanotubes containing more loosely bound Krn chains (n = 3–6). In some instances, delocalization of Kr atomic positions was confirmed by STEM analysis as the transition to a one-dimensional (1D) gas, as Kr atoms were constrained to only one degree of translational freedom within long, well-annealed, nested nanotubes. Such nested nanotube structures were investigated by Raman spectroscopy. This material represents a highly compressed and dimensionally constrained 1D gas stable under ambient conditions. Direct atomic-scale imaging has revealed elusive bonding states and a previously unseen 1D gaseous state of matter of this noble gas element, demonstrating TEM to be a powerful tool in the discovery of chemistry at the single-atom level.
carbon nanotubes, endohedral fullerenes, noble gases, one-dimensional gas, single-atom dynamics, time-resolved imaging, transmission electron microscopy
2958-2971
Cardillo-Zallo, Ian
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Biskupek, Johannes
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Bloodworth, Sally
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Marsden, Elizabeth S.
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Fay, Michael W.
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Ramasse, Quentin M.
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Rance, Graham A.
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Stoppiello, Craig T.
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Cull, William J.
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Weare, Benjamin L.
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Whitby, Richard J.
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Kaiser, Ute
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Brown, Paul D.
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Khlobystov, Andrei N.
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30 January 2024
Cardillo-Zallo, Ian
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Biskupek, Johannes
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Bloodworth, Sally
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Marsden, Elizabeth S.
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Fay, Michael W.
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Ramasse, Quentin M.
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Rance, Graham A.
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Stoppiello, Craig T.
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Cull, William J.
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Weare, Benjamin L.
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Whitby, Richard J.
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Kaiser, Ute
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Brown, Paul D.
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Khlobystov, Andrei N.
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Cardillo-Zallo, Ian, Biskupek, Johannes, Bloodworth, Sally, Marsden, Elizabeth S., Fay, Michael W., Ramasse, Quentin M., Rance, Graham A., Stoppiello, Craig T., Cull, William J., Weare, Benjamin L., Whitby, Richard J., Kaiser, Ute, Brown, Paul D. and Khlobystov, Andrei N.
(2024)
Atomic-scale time-resolved imaging of krypton dimers, chains and transition to a one-dimensional gas.
ACS Nano, 18 (4), .
(doi:10.1021/acsnano.3c07853).
Abstract
Single-atom dynamics of noble-gas elements have been investigated using time-resolved transmission electron microscopy (TEM), with direct observation providing for a deeper understanding of chemical bonding, reactivity, and states of matter at the nanoscale. We report on a nanoscale system consisting of endohedral fullerenes encapsulated within single-walled carbon nanotubes ((Kr@C60)@SWCNT), capable of the delivery and release of krypton atoms on-demand, via coalescence of host fullerene cages under the action of the electron beam (in situ) or heat (ex situ). The state and dynamics of Kr atoms were investigated by energy dispersive X-ray spectroscopy (EDS), electron energy loss spectroscopy (EELS), and X-ray photoelectron spectroscopy (XPS). Kr atom positions were measured precisely using aberration-corrected high-resolution TEM (AC-HRTEM), aberration-corrected scanning TEM (AC-STEM), and single-atom spectroscopic imaging (STEM-EELS). The electron beam drove the formation of 2Kr@C120 capsules, in which van der Waals Kr2 and transient covalent [Kr2]+ bonding states were identified. Thermal coalescence led to the formation of longer coalesced nested nanotubes containing more loosely bound Krn chains (n = 3–6). In some instances, delocalization of Kr atomic positions was confirmed by STEM analysis as the transition to a one-dimensional (1D) gas, as Kr atoms were constrained to only one degree of translational freedom within long, well-annealed, nested nanotubes. Such nested nanotube structures were investigated by Raman spectroscopy. This material represents a highly compressed and dimensionally constrained 1D gas stable under ambient conditions. Direct atomic-scale imaging has revealed elusive bonding states and a previously unseen 1D gaseous state of matter of this noble gas element, demonstrating TEM to be a powerful tool in the discovery of chemistry at the single-atom level.
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cardillo-zallo-et-al-2024-atomic-scale-time-resolved-imaging-of-krypton-dimers-chains-and-transition-to-a-one
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Accepted/In Press date: 2 January 2024
e-pub ahead of print date: 22 January 2024
Published date: 30 January 2024
Additional Information:
Funding information:
This work was supported by the Engineering and Physical Sciences Research Council (EPSRC), grant EP/V000055/1 for A.N.K., grant EP/W006413/1 for P.D.B., and grants EP/W021080/1 and EP/X035123/1 for Q.M.R., and work carried out at SuperSTEM, grants EP/P009980/1 and EP/T004320/1 for R.J.W., and the Molecular Imaging and Analysis DTP, project reference 2443531 for I.C.-Z. J.B. and U.K. (Ulm University) acknowledge the financial support of the German Research Foundation (DFG) within grant #424798828. W.J.C. acknowledges funding from the Leverhulme Trust, grant number RPG-2022-300: Taming the radicals: highly reactive species incarcerated in carbon cages. We are grateful to the Nottingham Nanoscale and Microscale Research Centre (nmRC) for access to equipment and the University of Nottingham for funding. The authors are grateful to I. Popov and R. Wheatley for helpful discussions.
Publisher Copyright:
© 2024 The Authors. Published by American Chemical Society.
Keywords:
carbon nanotubes, endohedral fullerenes, noble gases, one-dimensional gas, single-atom dynamics, time-resolved imaging, transmission electron microscopy
Identifiers
Local EPrints ID: 486450
URI: http://eprints.soton.ac.uk/id/eprint/486450
ISSN: 1936-0851
PURE UUID: 70bf7db8-2295-4eba-9e23-c70dd477b5bb
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Date deposited: 22 Jan 2024 17:59
Last modified: 13 Apr 2024 01:38
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Contributors
Author:
Ian Cardillo-Zallo
Author:
Johannes Biskupek
Author:
Elizabeth S. Marsden
Author:
Michael W. Fay
Author:
Quentin M. Ramasse
Author:
Graham A. Rance
Author:
Craig T. Stoppiello
Author:
William J. Cull
Author:
Benjamin L. Weare
Author:
Ute Kaiser
Author:
Paul D. Brown
Author:
Andrei N. Khlobystov
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