Compressibility behavior and pressure-induced over-hydration of zeolite K-AlSi-L

This paper reports a study, performed by in-situ synchrotron X-ray powder diffraction, of the high-pressure behavior of zeolite L. The experiments were performed using both penetrating (methanol: ethanol: water mixture, m.e.w.) and non-penetrating (silicon oil, s.o.) pressure transmitting media (PTM) to study the compressibility and the possible pressure-induced hydration (PIH) of this synthetic zeolite, technologically relevant as host-guest system exploited in numerous application fields. The experiments were performed from Pamb to 6.2 and 6.3 GPa in s.o. and m.e.w., respectively. The crystal structure refinements were performed up to 6.3 GPa and 3.1 GPa for the patterns collected in m.e.w. and s.o., respectively, while the unit cell parameters were determined in the whole pressure range for both media. A strong PIH effect is evident when zeolite L is compressed in m.e.w. and the over-hydration is essentially ascribable to the filling of most the H2O sites, to the appearance of a new H2O site and to the partially filling of the K sites. The over-hydration starts at a very low pressure (0.5 GPa) and the maximum H2O content can be estimated in 31.1 H2O molecules, against the original value of 18. The PIH is completely reversible upon P release. The main difference between the compression behavior of zeolite L in the two media is the higher compressibility in the non-penetrating one, evidenced by ΔV=− 6.3% and −9.9% in m.e.w. and s.o, respectively. Our data are consistent with the general behavior of zeolites compressed with penetrating media, when the intrusion of H2O molecules hinders the effects of the applied pressure. The results of this work are compared with those obtained on a K-gallosilicate with LTL topology, where PIH induces the formation of H2O nanotubes inside the zeolite channel.