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A solid-state nuclear magnetic resonance (NMR) experiment, which provides high-resolution two-dimensional heteronuclear correlation (HETCOR) spectra between 27Al and 31P, is described. The first part of the experiment uses triple-quantum or quintuple-quantum magic-angle spinning (MQMAS) NMR of spin-5/2 nuclei (27Al) to produce an isotropic echo that is unaffected by the second-order quadrupolar broadening. The magnetization is then transferred to the spin-1/2 (31P) nuclei via cross-polarization (CP), resulting in isotropic resolution in both spectral dimensions. To illustrate its usefulness, this method (referred to as MQHETCOR) is applied to two important microporous framework aluminophosphates, hydrated VPI-5 and AIPO4-40.

Abstract: Aluminum species in P-ZSM-5 zeolites were identified and quantified using 27Al MAS and MQMAS NMR methods. Samples containing between 0% and 15% P2O5 were studied after calcination or calcination followed by steaming. In addition to the tetrahedral framework aluminum, Altet-f, and the octahedral aluminum, Aloct, we also observed significant quantities of highly distorted aluminum with tetrahedral coordination, Altet-dis, and octahedrally coordinated aluminum in aluminum phosphate, Aloct-O-P. Furthermore, small quantities of the pentahedrally coordinated species Alpent-O-P were seen in samples with high phosphorus content. There was a good correlation between the amount of framework aluminum and acidity measured by TPD of n-propylamine. In contrast, the aluminum phosphate was shown to be catalytically inactive both by acidity measurements and catalytic tests. [Copyright &y& Elsevier]

Abstract: A suite of one- and two-dimensional solid-state NMR methods was used to follow the complex structural changes in different types of phosphorus species in P-ZSM-5 zeolites that were generated upon treatment of H-ZSM5 zeolites with 0–15% P2O5, followed by calcination or calcination and steaming. Through space and through bond 27Al–31P correlations were used for the first time to study the interaction of phosphorus with the aluminum species. Homogeneous impregnation of phosphorus inside the zeolite channels was observed even at low concentrations. In the calcined samples, the 31P resonances were assigned mainly to orthophosphates, short chain polyphosphates and condensed phosphates. These species were converted into various types of aluminum phosphates with steaming and with the increase in P content. The mechanisms of formation of phosphates and aluminum phosphates are proposed. [Copyright &y& Elsevier]

Solid-state nuclear magnetic resonance is used to study the thermal decomposition of lithium tetrahydroaluminate into metallic aluminum, hydrogen and trilithium hexahydroaluminate. Aluminum sites in LiAlH4 and Li3AlH6 were characterized using static, magic angle spinning (MAS) and multiple-quantum MAS NMR. By applying the in situ NMR method, it has been demonstrated that melting is not a prerequisite for the decomposition of LiAlH4. Based on the observed data, a decomposition path has been established that is consistent with the concentrations of observed Al species at various stages of the thermally induced reaction. [Copyright &y& Elsevier]