Heating-induced phase transformation in zeolite brewsterite: new 4- and 5-coordinated (Si,Al) sites

Abstract

The dehydration-rehydration processes and phase transformations of brewsterite (space group P21/m, ideal formula (Sr,Ba)Al2Si6O16·5H2O) were studied by single crystal X-ray diffraction on two samples heated in an evacuated capillary for 24 h at 280°C and 330°C, respectively, and then cooled to room temperature. After the data collection, the capillary of the crystal heated at 280°C was broken, the sample was kept at room conditions for one month, and diffraction data were recollected. Brewsterite heated in vacuum at 280°C shows a strong decrease of the unit cell volume (about 10%) and the statistical breaking of the T1-O7-T2 bridge of the 4-ring of the 4254 PBU. T1 cation, in 31% of cases, migrates to a new tetrahedral site, which shares three vertices with the previously occupied one; the fourth vertex is on the mirror plane, and joins two adjacent layers. T2 cation, in 20% of cases, migrates to a new site, which is characterized by a 5-fold coordination. This coordination polyhedron shares three vertices with the previously occupied tetrahedron; the fourth vertex is on the mirror plane, and joins two adjacent layers; the fifth one is unshared. The formation of these new T-O-T bridges prevents the re-expansion and rehydration of the heated brewsterite; as a consequence, the crystal brought back to room conditions does not show any noticeable structural difference with respect to that heated at 280°C. The exchangeable cations, which occupy only one extraframework site in the untreated brewsterite, spread over several sites. The sample heated at 330°C shows a further decrease in the unit cell volume of about 2% with respect to the sample heated at 280°C, and an increase in the migration percentage of T1 and T2 cations to the new sites.