Observation of Low-γ Quadrupolar Nuclei by Surface-Enhanced NMR Spectroscopy

Nagashima, Hiroki; Trebosc, Julien; Kon, Yoshihiro; Sato, Kazuhiko; Lafon, Olivier; Amoureux, Jean-Paul

Type de document :

Article dans une revue scientifique: Article original

DOI :

10.1021/jacs.9b13838

PMID :

32426972

URL permanente :

http://hdl.handle.net/20.500.12210/60631

Titre :

Observation of Low-γ Quadrupolar Nuclei by Surface-Enhanced NMR Spectroscopy

Auteur(s) :

Nagashima, Hiroki [Auteur]
Trebosc, Julien [Auteur]

Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Institut Michel Eugène Chevreul - FR 2638 [IMEC]
Kon, Yoshihiro [Auteur]
Sato, Kazuhiko [Auteur]
Lafon, Olivier [Auteur]

Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Institut universitaire de France [IUF]
Amoureux, Jean-Paul [Auteur]

Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Bruker

Titre de la revue :

Journal of the American Chemical Society

Nom court de la revue :

J. Am. Chem. Soc.

Numéro :

142

Pagination :

10659–10672

Éditeur :

American Chemical Society (ACS)

Date de publication :

2020-05-19

ISSN :

1520-5126

Mot(s)-clé(s) en anglais :

solid-state NMR
SENS
subsurface
half-integer quadrupolar nuclei
MoO3/TiO2

Discipline(s) HAL :

Chimie/Catalyse
Chimie/Chimie inorganique
Chimie/Chimie théorique et/ou physique

Résumé en anglais : [en]

We introduce a novel NMR approach that extends the capabilities of indirect dynamic nuclear polarization (DNP) under magic-angle spinning to probe the local environment of half-integer spin quadrupolar nuclei. Compared to ...
Lire la suite >We introduce a novel NMR approach that extends the capabilities of indirect dynamic nuclear polarization (DNP) under magic-angle spinning to probe the local environment of half-integer spin quadrupolar nuclei. Compared to cross-polarization, this novel method based on the refocused INEPT scheme with adiabatic dipolar recoupling is easier to optimize and does not distort the quadrupolar line shapes. Furthermore, the use of this technique, instead of the PRESTO (Phase-shifted Recoupling Effects a Smooth Transfer of Order) scheme or direct DNP, greatly improves the sensitivity of DNP-NMR for the detection of quadrupolar isotopes with small dipolar couplings to protons, including notably those located in the subsurface of inorganic materials or with low gyromagnetic ratio (γ). This technique has been applied to identify the atomic-level structure of Brønsted acid sites of hydrated titania-supported MoO3, MoO3/TiO2, a widely used heterogeneous catalyst. The spectra of protonated and unprotonated 17O sites, acquired in natural abundance, indicate the presence of various oxomolybdate species as well as HOMo2 and HOMo3 Brønsted acid sites. The enhanced sensitivity of this new method has also enabled the acquisition of the first DNP-enhanced spectra of 95Mo and 47,49Ti low-γ quadrupolar isotopes. This possibility has been demonstrated by detecting the signals of these nuclei near the surface of MoO3/TiO2. This technique has allowed the observation of 49Ti surface sites, which are absent from the bulk region of TiO2. Furthermore, both 95Mo and 47,49Ti DNP spectra have shown an increased structural disorder of TiO2 and MoO3 phases near the surface of the particles and notably the preferential location of the amorphous TiO2 phase at the surface of the particles. The proposed polarization transfer is also employed to acquire the first DNP-enhanced spectrum of 67Zn, another low-γ quadrupolar isotope. This possibility is demonstrated for Al-doped ZnO nanoparticles used in optoelectronic devices. The obtained 17O, 27Al, and 67Zn DNP-NMR data prove that the surface region of these nanoparticles contains ZnO phase as well as secondary phases, such as α-Al2O3 and partially inverse ZnAl2O4 spinel.Lire moins >

Langue :

Anglais

Comité de lecture :

Oui

Audience :

Internationale

Vulgarisation :

Non

Établissement(s) :

CNRS
Centrale Lille
ENSCL
Univ. Artois
Université de Lille

Collections :

Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181

Équipe(s) de recherche :

RMN et matériaux inorganiques (RM2I)

Date de dépôt :

2022-03-02T07:13:41Z
2023-03-17T15:27:10Z

Fichiers

20190909_OL_HN_ASR4_text-SI.pdf
Accès libre
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Numéro de version	Lien	Date de modification
2	20.500.12210/60631*	2023-03-17T14:20:53Z
1	20.500.12210/60631.1	2022-03-02T07:13:41Z

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Observation of Low-γ Quadrupolar Nuclei ...

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