Deuterium Exchange Dynamics in Zr_2NiD_(4.8) Studied by ^2H MAS NMR Spectroscopy

Abstract

Variable temperature (VT) ^2H magic angle spinning (MAS) spectroscopy was employed to measure deuterium diffusion behavior in the Zr_2NiD_(4.8) phase. ^2H MAS NMR spectrum at ∼190 K provides with well-resolved 4 different site occupancies which can be assigned based on the crystal structure (16k (Zr_2Ni_2), 32m (Zr_3Ni), Zr_4 (16/ and 4b)). As the temperature rises, the ^2H peaks sensitively reflect the exchange behavior among the sites with evident change at around 230 K and reaching a uniform distribution of site occupancies, indistinguishable in NMR timescale, above 245 K. This behavior is reflected by the collapse of the ^2H MAS spectrum into a single peak. From analyses of VT MAS NMR spectra, we were able to extract multiple hopping rates and activation energies among face sharing interstices: for example, 32m ↔ 16/ hopping shows _(τc)=2.8×10^(-4)s at 245 K and E_a = 62.2 kJ/mol.

Additional Information

© 2014 Elsevier. Available online 31 December 2014. This research was also supported by Basic Science Research Program through the National Research Foundation of Republic of Korea (NRF) funded by the Ministry of Education, Science and Technology (2010-0011558). This work was partially supported by DOE through Award Numbers DE-AI-01-05EE11105. The NMR facility at the California Institute of Technology was supported by the National Science Foundation (NSF) under Grant Number 9724240 and partially supported by the MRSEC Program of the NSF under Award Number DMR-520565.

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