Anion-promoted cation motion and conduction in zeolites.
The motion of sodium cations in sodalite and cancrinite has been investigated by force field calculations, solid-state NMR, and impedance spectroscopy. Special emphasis is dedicated to the influence of anions on sodium mobilities. Local cation motion is promoted when they interact with anions. However, not all systems with high local mobilities exhibit good ion conductivities, as cooperativity of the motion appears to be an important factor, as well. The activation barrier for local sodium motion (calculations) and long-range transport (dc conductivities) is lowered in sodalite when halogenide anions, Cl(-), Br(-), or I(-), are present. The activation barriers increase with increasing size of the anion and decreasing coordination in the transition state. On the basis of (23)Na solid-state NMR data, all the sodium ions in the dense sodalite structure are rather rigid up to 470 K. All the cations in chromate sodalite, and Na(+) in the small cancrinite epsilon-cages without anion interactions, show a restricted local motion at higher temperatures. There is a selective high local motion of Na(+) in the neighborhood of chromate anions in the more open channel system of cancrinite. These results suggest that sodium migration can be enhanced, at least locally, in open channel systems by anion interactions. A dynamics coupling between anion reorientation and cation mobility was not observed.
Jordan
Edgar
E
Institute of Physical Chemistry and Sonderforschungsbereich 458, University of Münster, Germany.
Bell
Robert G
RG
Wilmer
Dirk
D
Koller
Hubert
H