Differential penetration of ethanol and water in Si-chabazite: High pressure dehydration of azeotrope solution

This study is aimed to shed light on the mechanisms at the basis of the differential penetration of alcohol and water in hydrophobic zeolites at ambient (Pamb) and non-ambient pressure. Here we report the effects of the penetration of water and alcohol in an all-silica chabazite (Si-CHA) compressed with an ethanol/water azeotrope solution (ethanol: water = 95.63: 4.37 by mass %). We collected in situ synchrotron X-ray Powder Diffraction (XRPD) data in order to monitor the structural modifications induced by the fluid penetration and to investigate the guest-guest and host-guest interactions. First principles molecular dynamics simulations allowed to complete the structural description at high pressure, providing an atomistic level description of the guest-guest hydrogen bond network. For a comprehensive understanding of the processes involving the Si-CHA + azeotrope interactions, both the zeolite and the alcohol/water solution were firstly investigated separately under pressure. The results obtained prove that both H2O and ethanol penetrate Si-CHA porosities even at Pamb. However, while in these conditions the H2O/ethanol ratio adsorbed inside Si-CHA is similar to that of the external azeotrope solution, under pressure the zeolite extra-framework content corresponds to a composition much richer in H2O than the azeotrope one. Hence, our results suggest that a dehydration effect occurred on the azeotrope solution, promoted by pressure. In addition, the experiment performed to test the elastic behavior of Si-CHA with a non-penetrating pressure transmitting medium interestingly indicates that Si-pure chabazite is the most compressible zeolite among those up to now studied in silicone oil.