Insight into Hydrogen Bonding of Uranyl Hydroxide Layers and Capsules by Use of H Magic-Angle Spinning NMR Spectroscopy

نویسندگان

  • Todd M. Alam
  • Zuolei Liao
  • May Nyman
  • Jonathan Yates
چکیده

Solid-state H magic-angle spinning (MAS) NMR was used to investigate local proton environments in anhydrous [UO2(OH)2] (α-UOH) and hydrated uranyl hydroxide [(UO2)4O(OH)6·5H2O (metaschoepite). For the metaschoepite material, proton resonances of the μ2-OH hydroxyl and interlayer waters were resolved, with twodimensional (2D) double-quantum (DQ) H−H NMR correlation experiments revealing strong dipolar interactions between these different proton species. The experimental NMR results were combined with first-principles CASTEP GIPAW (gauge including projector-augmented wave) chemical shift calculations to develop correlations between hydrogenbond strength and observed H NMR chemical shifts. These NMR correlations allowed characterization of local hydrogenbond environments in uranyl U24 capsules and of changes in hydrogen bonding that occurred during thermal dehydration of metaschoepite.

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تاریخ انتشار 2016