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Issue 8, 2014
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Re-entrant layer reconstruction during intercalation in hafnium nitride chloride

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Abstract

An unprecedented re-entrant mechanism in which HfNCl host layers transform to an alternative geometry and then revert to their original structure, has been discovered during the synthesis of superconducting Na0.5HfNCl by ultra-slow electrochemical intercalation of sodium. Both the host and final product contain hexagonal β-HfNCl layers although the stacking sequence changes during a complex reaction sequence involving four intermediate phases. Restacking occurs through a displacive mechanism in which β-type layers transform to a different arrangement, most likely the rectangular layers found in the α-HfNCl polymorph, and then retransform to β-layers. These results reveal that intercalation reactions may proceed by very different mechanisms to those expected in the conventional ‘slab-gliding’ picture.

Graphical abstract: Re-entrant layer reconstruction during intercalation in hafnium nitride chloride

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Supplementary files

Article information


Submitted
14 Feb 2014
Accepted
30 Mar 2014
First published
31 Mar 2014

Chem. Sci., 2014,5, 2974-2978
Article type
Edge Article

Re-entrant layer reconstruction during intercalation in hafnium nitride chloride

V. Meignen, J. Oró-Solé, W. Bonin, M. Morcrette, M. R. Palacín, J. P. Attfield and A. Fuertes, Chem. Sci., 2014, 5, 2974
DOI: 10.1039/C4SC00499J

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