Effect of temperature and extraframework cation type on CHA framework flexibility

The sorption properties of zeolites are controlled by several factors, i.e. Si/Al ratio of the aluminosilicate framework [AlSiO₄]^-, the type and position of the extraframework (EF) cations, and the applied temperature. Here we investigate the flexibility of CHA framework as a function of EF cation-content and temperature (20-350 °C). Two CHA forms (Na- and Cu-CHA) with Si/Al = 2 were analysed. The main objectives were: (i) to shed light on the HT behaviour of Na-CHA, for which contrasting results exist in literature; (ii) define the role of temperature and EF cation-type in the response to the heating stimuli. We show that at 75 °C, Na-CHA undergoes a severe contraction of the unit-cell volume (-12%) accompanied by a symmetry lowering (R-3m to I2/m). The transformation is reversible, if the dehydrated Na-CHA is exposed to ambient conditions. In contrast, Cu-CHA experiences a significant different dehydration path, which involves minor changes of the CHA framework, and a net positive thermal-expansion after dehydration. The implications of the observed transformations for gas separation processes are finally discussed.