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Bond dissociation and reactivity of HF and H2O in a nano test tube

Bond dissociation and reactivity of HF and H2O in a nano test tube
Bond dissociation and reactivity of HF and H2O in a nano test tube
Molecular motion and bond dissociation are two of the most fundamental phenomena underpinning properties of molecular materials. We have entrapped HF and H2O molecules within the fullerene C60 cage, encapsulated within a single-walled carbon nanotube (X@C60)@SWNT where X = HF or H2O. (X@C60)@SWNT represents a class of molecular nanomaterial composed of a guest within a molecular host within a nanoscale host, enabling investigations of the interactions of isolated single di- or tri-atomic molecules with the electron beam. The use of the electron beam simultaneously as a stimulus of chemical reactions in molecules and as a sub-Å resolution imaging probe allows investigations of the molecular dynamics and reactivity in real time and at the atomic scale, which are probed directly by chromatic and spherical aberration corrected high resolution transmission electron microscopy (Cc/Cs-corrected HRTEM) imaging, or indirectly by vibrational electron energy loss spectroscopy (EELS) in situ during scanning transmission electron microscopy (STEM) experiments. Experimental measurements indicate that the electron beam triggers homolytic dissociation of the H-F or H-O bonds, respectively, causing the expulsion of the hydrogen atoms from the fullerene cage, leaving fluorine or oxygen behind. Due to a difference in the mechanisms of penetration through the carbon lattice available for F or O atoms, atomic fluorine inside the fullerene cage appears to be more stable than the atomic oxygen under the same conditions. The use of (X@C60)@SWNT, where each molecule X is ‘packaged’ separately from each other, in combination with the electron microscopy methods and density functional theory (DFT) modelling in this work, enable bond dynamics and reactivity of individual atoms to be probed directly at the single-molecule level.
DFT modelling, carbon nanotubes, endohedral fullerenes, single molecule dynamics, transmission electron microscopy
1936-0851
11178-11189
Biskupek, Johannes
7073737f-a487-4f37-ac7c-5aa185d36660
Skowron, Stephen T.
62c2c962-447f-4921-9c6e-f83be501476d
Stoppiello, Craig T.
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Rance, Graham A.
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Alom, Shamim
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Fung, Kayleigh L. Y.
5e3cab74-1a9b-4a2c-a60b-2ae56f3633f9
Whitby, Richard J.
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Levitt, Malcolm H.
bcc5a80a-e5c5-4e0e-9a9a-249d036747c3
Ramasse, Quentin M.
30aed351-dfed-4eea-9c87-375b75e24b79
Kaiser, Ute
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Besley, Elena
9628c33a-d2e2-478c-b357-b9eee8f31ba8
Khlobystov, Andrei N.
27b2c834-ce18-4106-9cbe-17e2968551a4
Biskupek, Johannes
7073737f-a487-4f37-ac7c-5aa185d36660
Skowron, Stephen T.
62c2c962-447f-4921-9c6e-f83be501476d
Stoppiello, Craig T.
91bf41e5-6073-482f-aa26-b8028aec7d3a
Rance, Graham A.
d0e90224-85ce-49cc-9280-67ec7ea727df
Alom, Shamim
f6b56fb1-7f94-432a-87cd-887f6e5d9f64
Fung, Kayleigh L. Y.
5e3cab74-1a9b-4a2c-a60b-2ae56f3633f9
Whitby, Richard J.
45632236-ab00-4ad0-a02d-6209043e818b
Levitt, Malcolm H.
bcc5a80a-e5c5-4e0e-9a9a-249d036747c3
Ramasse, Quentin M.
30aed351-dfed-4eea-9c87-375b75e24b79
Kaiser, Ute
4dc003b5-fa81-4993-9a12-5b60d0127c35
Besley, Elena
9628c33a-d2e2-478c-b357-b9eee8f31ba8
Khlobystov, Andrei N.
27b2c834-ce18-4106-9cbe-17e2968551a4

Biskupek, Johannes, Skowron, Stephen T., Stoppiello, Craig T., Rance, Graham A., Alom, Shamim, Fung, Kayleigh L. Y., Whitby, Richard J., Levitt, Malcolm H., Ramasse, Quentin M., Kaiser, Ute, Besley, Elena and Khlobystov, Andrei N. (2020) Bond dissociation and reactivity of HF and H2O in a nano test tube. ACS Nano, 14 (9), 11178-11189. (doi:10.1021/acsnano.0c02661).

Record type: Article

Abstract

Molecular motion and bond dissociation are two of the most fundamental phenomena underpinning properties of molecular materials. We have entrapped HF and H2O molecules within the fullerene C60 cage, encapsulated within a single-walled carbon nanotube (X@C60)@SWNT where X = HF or H2O. (X@C60)@SWNT represents a class of molecular nanomaterial composed of a guest within a molecular host within a nanoscale host, enabling investigations of the interactions of isolated single di- or tri-atomic molecules with the electron beam. The use of the electron beam simultaneously as a stimulus of chemical reactions in molecules and as a sub-Å resolution imaging probe allows investigations of the molecular dynamics and reactivity in real time and at the atomic scale, which are probed directly by chromatic and spherical aberration corrected high resolution transmission electron microscopy (Cc/Cs-corrected HRTEM) imaging, or indirectly by vibrational electron energy loss spectroscopy (EELS) in situ during scanning transmission electron microscopy (STEM) experiments. Experimental measurements indicate that the electron beam triggers homolytic dissociation of the H-F or H-O bonds, respectively, causing the expulsion of the hydrogen atoms from the fullerene cage, leaving fluorine or oxygen behind. Due to a difference in the mechanisms of penetration through the carbon lattice available for F or O atoms, atomic fluorine inside the fullerene cage appears to be more stable than the atomic oxygen under the same conditions. The use of (X@C60)@SWNT, where each molecule X is ‘packaged’ separately from each other, in combination with the electron microscopy methods and density functional theory (DFT) modelling in this work, enable bond dynamics and reactivity of individual atoms to be probed directly at the single-molecule level.

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Accepted/In Press date: 12 August 2020
e-pub ahead of print date: 20 August 2020
Published date: 22 September 2020
Keywords: DFT modelling, carbon nanotubes, endohedral fullerenes, single molecule dynamics, transmission electron microscopy

Identifiers

Local EPrints ID: 443434
URI: http://eprints.soton.ac.uk/id/eprint/443434
ISSN: 1936-0851
PURE UUID: 5d0f814f-53c1-4910-bc7b-9dc9f013a8aa
ORCID for Richard J. Whitby: ORCID iD orcid.org/0000-0002-9891-5502
ORCID for Malcolm H. Levitt: ORCID iD orcid.org/0000-0001-9878-1180

Catalogue record

Date deposited: 25 Aug 2020 16:31
Last modified: 26 Nov 2021 05:57

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Contributors

Author: Johannes Biskupek
Author: Stephen T. Skowron
Author: Craig T. Stoppiello
Author: Graham A. Rance
Author: Shamim Alom
Author: Kayleigh L. Y. Fung
Author: Quentin M. Ramasse
Author: Ute Kaiser
Author: Elena Besley
Author: Andrei N. Khlobystov

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