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Scandium and Yttrium Environments in Aluminosilicate Glasses Unveiled by Sc-45/Y-89 NMR Spectroscopy and DFT Calculations: What Structural Factors Dictate the Chemical Shifts?
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Number of Authors: 4
2017 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 121, no 34, 18815-18829 p.Article in journal (Refereed) Published
Abstract [en]

Aluminosilicate (AS) glasses incorporating rare-earth (RE) elements exhibit favorable mechanical and (magneto)optical properties that reflect their unusual structural Organization. Yet, experimental reports on the local RE3+ environments in AS glasses are very sparse. We examine the Y3+ and Sc3+ cations in Y2O3-Al2O3-SiO2 and Sc2O3-Al2O3-SiO2 glasses of variable RE/Al/Si contents by utilizing magic-angle spinning (MAS) Y-89 and Sc-45 nuclear magnetic resonance (NMR) experiments coupled with density functional theory (DFT) calculations of Y-89/Sc-45 NMR chemical shifts. The DFT models reveal {Y-[p]} and {Sc-[p]} coordination numbers (p) spanning 5 <= p <= 8 and 4 <= p <= 7, respectively; with {Y-[6], Y-[7] and {Sc-[5], Sc-[6]} species dominating. Wide isotropic chemical shift ranges of 35-354 ppm (Y-89) and'48-208 ppm (Sc-45) are observed, as well as sizable shift'anisotropies up to approximate to 370 ppm and approximate to 250 ppm for Y-89 and Sc-45, respectively. Both the isotropic and anisotropic chemical shifts grow when the coordination number p is decreased for Y-89([p]) as well as Sc-45([p]). Second to the coordination number, we demonstrate that the Y-89/Sc-45 isotropic chemical shifts are mainly influenced by the RE/Al/Si constellation in the second coordination sphere of Y and Sc; where the shift tends to increase for emphasized contacts with neighboring RE and Al species at the expense of Si. These DFT-derived trends are corroborated by a progressive 89Y deshielding observed in MAS Y-89 NMR spectra for increasing Y and/or Al content of the glass. We also introduce heteronuclear MAS NMR experimentation involving the pairs of Y-89-Al-27 and Sc-45-Si-29 nuclides, utilized for probing the contacts between the Y3+/Sc3+ cations and the AS glass-network forming groups.

Place, publisher, year, edition, pages
2017. Vol. 121, no 34, 18815-18829 p.
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:su:diva-147900DOI: 10.1021/acs.jpcc.7b05471ISI: 000409395700055OAI: oai:DiVA.org:su-147900DiVA: diva2:1150678
Available from: 2017-10-19 Created: 2017-10-19 Last updated: 2017-10-19Bibliographically approved

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Jaworski, AleksanderCharpentier, ThibaultStevensson, BaltzarEdén, Mattias
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