In Situ Multinuclear Magic-Angle Spinning NMR: Monitoring Crystallization of Molecular Sieve AlPO₄-11 in Real Time

Molecular sieves are crystalline three-dimensional frameworks with well-defined channels and cavities. They have been widely used in industry for many applications such as gas separation/purification, ion exchange, and catalysis. Obviously, understanding the formation mechanisms is fundamentally important. High-resolution solid-state NMR spectroscopy is a powerful method for the study of molecular sieves. However, due to technical challenges, the vast majority of the high-resolution solid-state NMR studies on molecular sieve crystallization are ex situ. In the present work, using a new commercially available NMR rotor that can withhold high pressure and high temperature, we examined the formation of molecular sieve AlPO₄-11 under dry gel conversion conditions by in situ multinuclear (¹H, ²⁷Al, ³¹P, and ¹³C) magic-angle spinning (MAS) solid-state NMR. In situ high-resolution NMR spectra obtained as a function of heating time provide much insights underlying the crystallization mechanism of AlPO₄-11. Specifically, in situ ²⁷Al and ³¹P MAS NMR along with ¹H → ³¹P cross-polarization (CP) MAS NMR were used to monitor the evolution of the local environments of framework Al and P, in situ ¹H → ¹³C CP MAS NMR to follow the behavior of the organic structure directing agent, and in situ ¹H MAS NMR to unveil the effect of water content on crystallization kinetics. The in situ MAS NMR results lead to a better understanding of the formation of AlPO₄-11.