Structure of an aluminophosphate EMM-8: a multi-technique approach

The crystal structure of an aluminophosphate, EMM-8 (ExxonMobil Material #8), was determined in its calcined, anhydrous form from synchrotron powder diffraction data using the computer program FOCUS. A linkage of double four-ring (D4R) building units forms a two-dimensional framework with 12-MR and 8-MR channels, and differs from a similar SAPO-40 (AFR) framework only by the relationship between paired D4R units. Rietveld refinement reveals a fit of the model to the observed synchrotron data by R wp = 0.1118, R(F 2) = 0.1769. Local environments of the tetrahedral phosphorus and aluminium sites were established by solid-state NMR, which detects distinct differences between as-synthesized and calcined materials. Distinct, reversible changes in the local symmetry of the P and Al atoms were observed by NMR upon calcination and subsequent hydration. These NMR data provided important constraints on the number of tetrahedral (T) atoms per unit cell and the connectivities of the T atoms. Detailed local structural information obtained by solid-state NMR thereby guided the ultimate determination of the structure of AlPO EMM-8 from the powder data. Comparisons are made to the recently published crystal structure of the fluoride-containing, as-synthesized SSZ-51, indicating that the unit-cell symmetry, axial dimensions and framework structure are preserved after calcination.