1D and 2D solid state NMR investigations of the framework structure of As-synthesized AlPO 4-14

Abstract

The framework structure of As-synthesized A1PO 4-14 has been investigated with a combination of different one-dimensional 27Al and 31P solid state NMR techniques and 27Al 31P double resonance methods. The results are found to be fully consistent with the assumed structural model. 27Al MAS and DOR experiments at three different magnetic field strengths together with simulations show the presence of two tetrahedral sites, one pentacoordinated and one octahedral aluminum site. The 27Al quadrupolar coupling constants and the 31P isotropic chemical shifts of the tetrahedral sites correlate well with tetrahedral shear-strain parameters and mean P-O-A1 bond angles, respectively. These correlations allow one to assign all of the NMR resonances to specific T-sites in the proposed framework structure. The assignments are then further confirmed by the application of three different two-dimensional heteronuclear correlation methods (i.e., 27Al → 31P TEDOR, CP, and INEPT) which reveal the connectivities between AlO x and PO 4 polyhedra. The two-dimensional INEPT experiment is applied here for the first time in the solid state.