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Direct 17O isotopic labeling of oxides using mechanochemistry

Direct 17O isotopic labeling of oxides using mechanochemistry
Direct 17O isotopic labeling of oxides using mechanochemistry

While 17O NMR is increasingly being used for elucidating the structure and reactivity of complex molecular and materials systems, much effort is still required for it to become a routine analytical technique. One of the main difficulties for its development comes from the very low natural abundance of 17O (0.04%), which implies that isotopic labeling is generally needed prior to NMR analyses. However, 17O-enrichment protocols are often unattractive in terms of cost, safety, and/or practicality, even for compounds as simple as metal oxides. Here, we demonstrate how mechanochemistry can be used in a highly efficient way for the direct 17O isotopic labeling of a variety of s-, p-, and d-block oxides, which are of major interest for the preparation of functional ceramics and glasses: Li2O, CaO, Al2O3, SiO2, TiO2, and ZrO2. For each oxide, the enrichment step was performed under ambient conditions in less than 1 h and at low cost, which makes these synthetic approaches highly appealing in comparison to the existing literature. Using high-resolution solid-state 17O NMR and dynamic nuclear polarization, atomic-level insight into the enrichment process is achieved, especially for titania and alumina. Indeed, it was possible to demonstrate that enriched oxygen sites are present not only at the surface but also within the oxide particles. Moreover, information on the actual reactions occurring during the milling step could be obtained by 17O NMR, in terms of both their kinetics and the nature of the reactive species. Finally, it was demonstrated how high-resolution 17O NMR can be used for studying the reactivity at the interfaces between different oxide particles during ball-milling, especially in cases when X-ray diffraction techniques are uninformative. More generally, such investigations will be useful not only for producing 17O-enriched precursors efficiently but also for understanding better mechanisms of mechanochemical processes themselves.

0020-1669
13050-13066
Chen, Chia Hsin
c18a6d62-5d94-4f75-9bb9-1add0e170021
Gaillard, Emeline
c1067cae-94af-4684-88a6-744ba33ff60c
Mentink-Vigier, Frédéric
6d108ac1-11ba-41c7-b66e-80e78a2f829a
Chen, Kuizhi
4eaa4984-2549-4aa6-8c70-944d62950492
Gan, Zhehong
b0d2481e-2f80-41e6-b28e-06f165c3534f
Gaveau, Philippe
df8d89a8-a4d4-4b17-9a65-5cd44830a94c
Rebière, Bertrand
2831ac88-fc12-4edb-a4f4-338ec31d5938
Berthelot, Romain
4ff31368-4de3-46d4-bd91-39a876820364
Florian, Pierre
e2526213-cc69-4bbb-9c0d-7b3f280a5ca5
Bonhomme, Christian
546cdb7b-d2a5-4428-9a51-1d060703d50b
Smith, Mark E.
abd04fbf-5f56-459d-89ec-e51ab2598c09
Métro, Thomas Xavier
136f3d92-1617-437c-b4a6-c34317ea34f3
Alonso, Bruno
7a2e9f7c-4ab2-4ffe-ae84-b84c6a10e148
Laurencin, Danielle
5f5fceb8-0be6-4a68-abf6-7dc66068db63
Chen, Chia Hsin
c18a6d62-5d94-4f75-9bb9-1add0e170021
Gaillard, Emeline
c1067cae-94af-4684-88a6-744ba33ff60c
Mentink-Vigier, Frédéric
6d108ac1-11ba-41c7-b66e-80e78a2f829a
Chen, Kuizhi
4eaa4984-2549-4aa6-8c70-944d62950492
Gan, Zhehong
b0d2481e-2f80-41e6-b28e-06f165c3534f
Gaveau, Philippe
df8d89a8-a4d4-4b17-9a65-5cd44830a94c
Rebière, Bertrand
2831ac88-fc12-4edb-a4f4-338ec31d5938
Berthelot, Romain
4ff31368-4de3-46d4-bd91-39a876820364
Florian, Pierre
e2526213-cc69-4bbb-9c0d-7b3f280a5ca5
Bonhomme, Christian
546cdb7b-d2a5-4428-9a51-1d060703d50b
Smith, Mark E.
abd04fbf-5f56-459d-89ec-e51ab2598c09
Métro, Thomas Xavier
136f3d92-1617-437c-b4a6-c34317ea34f3
Alonso, Bruno
7a2e9f7c-4ab2-4ffe-ae84-b84c6a10e148
Laurencin, Danielle
5f5fceb8-0be6-4a68-abf6-7dc66068db63

Chen, Chia Hsin, Gaillard, Emeline, Mentink-Vigier, Frédéric, Chen, Kuizhi, Gan, Zhehong, Gaveau, Philippe, Rebière, Bertrand, Berthelot, Romain, Florian, Pierre, Bonhomme, Christian, Smith, Mark E., Métro, Thomas Xavier, Alonso, Bruno and Laurencin, Danielle (2020) Direct 17O isotopic labeling of oxides using mechanochemistry. Inorganic Chemistry, 59 (18), 13050-13066. (doi:10.1021/acs.inorgchem.0c00208).

Record type: Article

Abstract

While 17O NMR is increasingly being used for elucidating the structure and reactivity of complex molecular and materials systems, much effort is still required for it to become a routine analytical technique. One of the main difficulties for its development comes from the very low natural abundance of 17O (0.04%), which implies that isotopic labeling is generally needed prior to NMR analyses. However, 17O-enrichment protocols are often unattractive in terms of cost, safety, and/or practicality, even for compounds as simple as metal oxides. Here, we demonstrate how mechanochemistry can be used in a highly efficient way for the direct 17O isotopic labeling of a variety of s-, p-, and d-block oxides, which are of major interest for the preparation of functional ceramics and glasses: Li2O, CaO, Al2O3, SiO2, TiO2, and ZrO2. For each oxide, the enrichment step was performed under ambient conditions in less than 1 h and at low cost, which makes these synthetic approaches highly appealing in comparison to the existing literature. Using high-resolution solid-state 17O NMR and dynamic nuclear polarization, atomic-level insight into the enrichment process is achieved, especially for titania and alumina. Indeed, it was possible to demonstrate that enriched oxygen sites are present not only at the surface but also within the oxide particles. Moreover, information on the actual reactions occurring during the milling step could be obtained by 17O NMR, in terms of both their kinetics and the nature of the reactive species. Finally, it was demonstrated how high-resolution 17O NMR can be used for studying the reactivity at the interfaces between different oxide particles during ball-milling, especially in cases when X-ray diffraction techniques are uninformative. More generally, such investigations will be useful not only for producing 17O-enriched precursors efficiently but also for understanding better mechanisms of mechanochemical processes themselves.

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e-pub ahead of print date: 13 March 2020
Published date: 21 September 2020

Identifiers

Local EPrints ID: 441456
URI: http://eprints.soton.ac.uk/id/eprint/441456
ISSN: 0020-1669
PURE UUID: 6fa27e8d-ed6b-44cd-8db3-1ddde2881a43

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Date deposited: 12 Jun 2020 16:40
Last modified: 26 Nov 2020 17:32

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Contributors

Author: Chia Hsin Chen
Author: Emeline Gaillard
Author: Frédéric Mentink-Vigier
Author: Kuizhi Chen
Author: Zhehong Gan
Author: Philippe Gaveau
Author: Bertrand Rebière
Author: Romain Berthelot
Author: Pierre Florian
Author: Christian Bonhomme
Author: Mark E. Smith
Author: Thomas Xavier Métro
Author: Bruno Alonso
Author: Danielle Laurencin

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