Distribution of Aluminum Species in Zeolite Catalysts: 27Al NMR of Framework, Partially-Coordinated Framework, and Non-Framework Moieties

The structure of aluminum-containing moieties in and within zeolite H-ZSM-5 catalysts is a complex function of the elemental composition of the catalyst, synthesis conditions, exposure to moisture, and thermal history. ²⁷Al NMR data collected at field strengths ranging from 7.05 to 35.2 T, i.e., ¹H Larmor frequencies from 300 to 1500 MHz, reveal that Al primarily exists as framework or partially coordinated framework species in commercially available dehydrated H-ZSM-5 catalysts with Si/Al ranging from 11.5 to 40. Quantitative direct-excitation and sensitivity-enhanced ²⁷Al NMR techniques applied over the wide range of magnetic field strengths used in this study show that prior to significant hydrothermal exposure, detectable amounts of nonframework Al species do not exist. Two-dimensional ²⁷Al multiple-quantum magic-angle spinning (MQMAS) along with ¹H-²⁷Al and ²⁹Si-²⁷Al dipolar correlation (D-HMQC) NMR experiments confirm this conclusion and show that generation of nonframework species following varying severities of hydrothermal exposure are clearly resolved from partially coordinated framework sites. The impact of hydration on the appearance and interpretation of conventional direct-excitation ²⁷Al spectra, commonly used to assess framework and nonframework Al, is discussed. Aluminum sites in dehydrated catalysts, which are representative of typical operating conditions, are characterized by large quadrupole interactions and are best assigned by obtaining data at multiple field strengths. On the basis of the results here, an accurate initial assessment of Al sites in high-Al content MFI catalysts prior to any hydrothermal treatment can be used to guide reaction conditions, anticipate potential water impacts, and identify contributions from hydroxyl groups other than those associated with the framework bridging acid site.