NMR study of reorientational motion in alkaline-earth borohydrides: β and γ phases of Mg(BH 4) 2 and α and β Phases of Ca(BH 4) 2
(2012) The Journal of Physical Chemistry Part C: Nanomaterials and Interfaces — Vol. 116, n° 7, p. 4913-4920 (2012)
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- To study the reorientational motion of BH 4 groups in β and γ phases of Mg(BH 4) 2 and in α and β phases of Ca(BH 4) 2, we have performed nuclear magnetic resonance (NMR) measurements of the 1H and 11B spin-lattice relaxation rates in these compounds over wide ranges of temperature and resonance frequency. It is found that at low temperatures the reorientational motion in β phases of Mg(BH 4) 2 and Ca(BH 4) 2 is considerably faster than in other studied phases of these alkaline-earth borohydrides. The behavior of the measured spin-lattice relaxation rates in both β phases can be satisfactorily described in terms of a Gaussian distribution of activation energies E a with the average E a values of 138 meV for β-Mg(BH 4) 2 and 116 meV for β-Ca(BH 4) 2. The α phase of Ca(BH 4) 2 is characterized by the activation energy of 286 ± 7 meV. For the novel porous γ phase of Mg(BH 4) 2, the main reorientational process responsible for the observed spin-lattice relaxation rate maximum can be described by the activation energy of 276 ± 5 meV. The barriers for reorientational motion in different phases of alkaline-earth borohydrides are discussed on the basis of changes in the local environment of BH 4 groups. © 2012 American Chemical Society.
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Soloninin, A. V., Babanova, O. A., Skripov, A. V., Hagemann, H., Richter, B., Jensen, T. R., & Filinchuk, Y. (2012). NMR study of reorientational motion in alkaline-earth borohydrides: β and γ phases of Mg(BH 4) 2 and α and β Phases of Ca(BH 4) 2. The Journal of Physical Chemistry Part C: Nanomaterials and Interfaces, 116(7), 4913-4920. https://doi.org/10.1021/jp210509g (Original work published 2012)