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

Autor: Philippe Gaveau, Dinu Iuga, Emilie Thomassot, Julien Trébosc, Danielle Laurencin, Mark E. Smith, Nicolas Fabregue, Frederic Mentink-Vigier, Ieva Goldberga, Thomas-Xavier Métro, Kuizhi Chen, Zhehong Gan, Chia-Hsin Chen, Bruno Alonso
Přispěvatelé: Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), National High Magnetic Field Laboratory (NHMFL), Florida State University [Tallahassee] (FSU), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Institut Michel Eugène Chevreul - FR 2638 (IMEC), Université d'Artois (UA)-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Centrale Lille Institut (CLIL), Centre de Recherches Pétrographiques et Géochimiques (CRPG), Institut national des sciences de l'Univers (INSU - CNRS)-Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), University of Warwick [Coventry], University of Southampton, Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)
Jazyk: angličtina
Rok vydání: 2021
Předmět:
Zdroj: Chemistry – A European Journal
Chemistry-A European Journal
Chemistry-A European Journal, Wiley-VCH Verlag, 2021, 27 (49), pp.12574-12588. ⟨10.1002/chem.202101421⟩
Chemistry (Weinheim an Der Bergstrasse, Germany)
Chemistry-A European Journal, 2021, 27 (49), pp.12574-12588. ⟨10.1002/chem.202101421⟩
ISSN: 0947-6539
1521-3765
Popis: 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.
A fast, user‐friendly17O enrichment approach by ball milling was developed to selectively enrich the surface of fumed silica. A variety of high‐resolution solid‐state 17O NMR experiments (ultra‐high magnetic field (35.2 T), 17O MQMAS, 2D 17O−1H D‐HMQC, 17O DNP), demonstrate that siloxane and different silanol bonds present at the surface, including H‐bonded and isolated silanols, can be labeled and characterized in detail.
Databáze: OpenAIRE
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