Improved Understanding of Atomic Ordering in Y4SixAl2- xO9- xNxMaterials Using a Combined Solid-State NMR and Computational Approach

Seymour, V.R. and Griffin, J.M. and Griffith, B.E. and Page, S.J. and Iuga, D. and Hanna, J.V. and Smith, M.E. (2020) Improved Understanding of Atomic Ordering in Y4SixAl2- xO9- xNxMaterials Using a Combined Solid-State NMR and Computational Approach. The Journal of Physical Chemistry C, 124 (43). pp. 23976-23987. ISSN 1932-7447

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Ceramics based around silicon aluminum oxynitrides are of both fundamental structural chemistry and technological interest. Certain oxynitride crystal structures allow very significant compositional variation through extensive Si/N exchange for Al/O, which implies a degree of atomic ordering. In this study, solid-state 29Si MAS NMR and variable field 1D and 2D 27Al MAS NMR measurements are combined with density functional theory calculations of both the structural and NMR interaction parameters for various points across the Y4Si2O7N2-Y4Al2O9 compositional range. This series provides numerous possibilities for significant variation of atomic ordering in the local ditetrahedral (Si,Al)2O7-xNx units. The two slightly structurally inequivalent aluminum sites in Y4Al2O9 are unambiguously assigned to the observed resonances. Computational findings on Y4Si2O7N2 demonstrate that the single observed 29Si NMR resonance covers a range of local inequivalent silicon environments. For the first time, the MAS NMR and neutron diffraction data from the Y4SiAlO8N structure have been directly reconciled, thus establishing aspects of atomic order and disorder that characterize this system. This comparison suggests that, although the diffraction data indicates long-range structural order supporting a highly crystalline character, the short-range information afforded by the solid-state NMR measurements indicates significant atomic disorder throughout the (Si,Al)2O7-xNx units.

Item Type:
Journal Article
Journal or Publication Title:
The Journal of Physical Chemistry C
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This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see
Uncontrolled Keywords:
?? aluminum compoundsatomsceramic materialscomputation theorycrystal atomic structuredensity functional theorylight polarizationneutron diffractionnuclear magnetic resonancenuclear magnetic resonance spectroscopycompositional rangecompositional variationcomp ??
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15 Dec 2020 13:21
Last Modified:
07 Nov 2023 01:05