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Labeling and probing the silica surface using mechanochemistry and 17O NMR spectroscopy

Labeling and probing the silica surface using mechanochemistry and 17O NMR spectroscopy
Labeling and probing the silica surface using mechanochemistry and 17O NMR spectroscopy
In recent years, there has been increasing interest in developing cost-efficient, fast, and user-friendly 17O enrichment protocols to help to understand the structure and reactivity of materials by using 17O NMR spectroscopy. Here, we show for the first time how ball milling (BM) can be used to selectively and efficiently enrich the surface of fumed silica, which is widely used at industrial scale. Short milling times (up to 15 min) allowed modulation of the enrichment level (up to ca. 5 %) without significantly changing the nature of the material. High-precision 17O compositions were measured at different milling times by using large-geometry secondary-ion mass spectrometry (LG-SIMS). High-resolution 17O NMR analyses (including at 35.2 T) allowed clear identification of the signals from siloxane (Si−O−Si) and silanols (Si−OH), while DNP analyses, performed by using direct 17O polarization and indirect 17O{1H} CP excitation, agreed with selective labeling of the surface. Information on the distribution of Si−OH environments at the surface was obtained from 2D 1H−17O D-HMQC correlations. Finally, the surface-labeled silica was reacted with titania and using 17O DNP, their common interface was probed and Si−O−Ti bonds identified.
17O, mechanochemistry, silica, solid state nmr spectroscopy, surface chemistry
0947-6539
12574-12588
Chen, Chia Hsin
c18a6d62-5d94-4f75-9bb9-1add0e170021
Mentink-Vigier, Frédéric
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Trébosc, Julien
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Goldberga, Ieva
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Gaveau, Philippe
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Thomassot, Emilie
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Iuga, Dinu
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Smith, Mark
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Chen, Kuizhi
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Gan, Zhehong
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Fabregue, Nicolas
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Métro, Thomas Xavier
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Alonso, Bruno
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Laurencin, Danielle
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Chen, Chia Hsin
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Mentink-Vigier, Frédéric
6d108ac1-11ba-41c7-b66e-80e78a2f829a
Trébosc, Julien
87552ef7-62a1-4f20-9445-891ad6effcb9
Goldberga, Ieva
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Gaveau, Philippe
df8d89a8-a4d4-4b17-9a65-5cd44830a94c
Thomassot, Emilie
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Iuga, Dinu
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Smith, Mark
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Chen, Kuizhi
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Gan, Zhehong
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Fabregue, Nicolas
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Métro, Thomas Xavier
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Alonso, Bruno
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Laurencin, Danielle
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Chen, Chia Hsin, Mentink-Vigier, Frédéric, Trébosc, Julien, Goldberga, Ieva, Gaveau, Philippe, Thomassot, Emilie, Iuga, Dinu, Smith, Mark, Chen, Kuizhi, Gan, Zhehong, Fabregue, Nicolas, Métro, Thomas Xavier, Alonso, Bruno and Laurencin, Danielle (2021) Labeling and probing the silica surface using mechanochemistry and 17O NMR spectroscopy. Chemistry - A European Journal, 27 (49), 12574-12588. (doi:10.1002/chem.202101421).

Record type: Article

Abstract

In recent years, there has been increasing interest in developing cost-efficient, fast, and user-friendly 17O enrichment protocols to help to understand the structure and reactivity of materials by using 17O NMR spectroscopy. Here, we show for the first time how ball milling (BM) can be used to selectively and efficiently enrich the surface of fumed silica, which is widely used at industrial scale. Short milling times (up to 15 min) allowed modulation of the enrichment level (up to ca. 5 %) without significantly changing the nature of the material. High-precision 17O compositions were measured at different milling times by using large-geometry secondary-ion mass spectrometry (LG-SIMS). High-resolution 17O NMR analyses (including at 35.2 T) allowed clear identification of the signals from siloxane (Si−O−Si) and silanols (Si−OH), while DNP analyses, performed by using direct 17O polarization and indirect 17O{1H} CP excitation, agreed with selective labeling of the surface. Information on the distribution of Si−OH environments at the surface was obtained from 2D 1H−17O D-HMQC correlations. Finally, the surface-labeled silica was reacted with titania and using 17O DNP, their common interface was probed and Si−O−Ti bonds identified.

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e-pub ahead of print date: 15 June 2021
Keywords: 17O, mechanochemistry, silica, solid state nmr spectroscopy, surface chemistry

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Local EPrints ID: 450564
URI: http://eprints.soton.ac.uk/id/eprint/450564
ISSN: 0947-6539
PURE UUID: 82d1a12c-66d0-4e1a-9a3a-14d81ccf49f2

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Date deposited: 04 Aug 2021 16:31
Last modified: 21 Oct 2021 17:20

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Contributors

Author: Chia Hsin Chen
Author: Frédéric Mentink-Vigier
Author: Julien Trébosc
Author: Ieva Goldberga
Author: Philippe Gaveau
Author: Emilie Thomassot
Author: Dinu Iuga
Author: Mark Smith
Author: Kuizhi Chen
Author: Zhehong Gan
Author: Nicolas Fabregue
Author: Thomas Xavier Métro
Author: Bruno Alonso
Author: Danielle Laurencin

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