Pressure-Induced Amorphization of Small Pore Zeolites-the Role of Cation-H2O Topology and Anti-glass Formation

Systematic studies of pressure-induced amorphization of natrolites (PIA) containing monovalent extra-framework cations (EFC) Li+, Na+, K+, Rb+, Cs+ allow us to assess the role of two different EFC-H2O configurations within the pores of a zeolite: one arrangement has H2O molecules (NATI) and the other the EFC (NAT(II)) in closer proximity to the aluminosilicate framework. We show that NAT(I) materials have a lower onset pressure of PIA than the NAT(II) materials containing Rb and Cs as EFC. The onset pressure of amorphization (P-A) of NAT(II) materials increases linearly with the size of the EFC, whereas their initial bulk moduli (P-1 phase) decrease linearly. Only Cs- and Rb-NAT reveal a phase separation into a dense form (P-2 phase) under pressure. High-Angle Annular Dark Field Scanning Transmission Electron Microscopy (HAADF-STEM) imaging shows that after recovery from pressures near 25 and 20 GPa long-range ordered Rb-Rb and Cs-Cs correlations continue to be present over length scales up to 100 nm while short-range ordering of the aluminosilicate framework is significantly reduced-this opens a new way to form anti-glass structuresopen