Compressibility of microporous materials with CHA topology: 2. ALPO-34

The HP behavior of ALPO-34 as-synthesized was investigated by means of in-situ synchrotron X-ray powder diffraction, in the frame of a wider project aimed at understanding the role of the framework/extraframework content in the P-induced deformation mechanisms of natural and synthetic microporous materials with CHA framework topology. ALPO-34 compressibility under non-penetrating P-transmitting medium was determined up to 6.0 GPa and upon decompression to P-amb. After an initial large structure deformation at P < 0.4 GPa, a regular volume reduction was observed up to about 3 GPa. Above 3.1 GPa, an abrupt change in the behavior of all cell parameters was observed, accompanied by an evident decrease in compressibility. The isothermal Equation of State (EoS), refined with a II-order Birch-Murnaghan EoS from 0.4 to 3.1 GPa, yielded the following parameters: V-0 = 755(1) angstrom(3), K-0 = 54(3) GPa. No complete X-ray amorphization was achieved up to the highest investigated P value. A complete reversibility of the unit cell parameters was observed upon P release. The compressibility behavior of ALPO-34 was compared with that of the other CHA-type zeolites. The volume reduction observed for natural chabazite, and for SAPO-34 and ALPO-34 as-synthesized, was 6.2%, 9.4%, and 6.0%, respectively. Notwithstanding the presence of morpholine molecules, as a structure directing agent, in the two as-synthesized phases, they exhibited significantly different compressibility. This can be interpreted as due to the octahedral coordination of part of the ALPO-34 framework aluminum, leading to a more rigid framework compared to that of SAPO-34, which contains only tetrahedral aluminum.