Structure and Framework Association of Lewis Acid Sites in MOR Zeolite.

Zeolites, although key materials used in industrial processes, remain poorly understood on a molecular level despite their well-defined crystal lattices. In fact, obtaining a direct spectroscopic signatures and resolving the structure of Lewis acid sites (LAS) has remained a challenge. In this work, thanks to 1D and 2D 1 H, 15 N, and 27 Al MAS NMR spectroscopy, carried out at different temperatures (from 298 down to 107 K), we were able to obtain the NMR spectroscopic signatures of LAS and Brønsted acid sites (BAS) in mordenite zeolite in the presence and the absence of adsorbed pyridine (Py). Combined with DFT modeling, this information enabled the structure of LAS to be revealed, namely (≡SiO) 3 Al sites interacting with pyridine, thus indicating that the corresponding base-free framework-associated sites are pseudo tricoordinated Al sites, namely tricoordinated Al sites interacting with an additional coordinated adjacent siloxane bridge. With this information in hand, we propose a molecular-level understanding on how the Al IV and Al VI framework and framework-associated sites evolve upon dehydration and exposure to Py into BAS and LAS, and their associated Py adducts. By measuring and analyzing the changes in quadrupolar coupling constants (C Q ) that reflect electrical charge distribution around the nuclei, we further show that the lower C Q values observed at 298 K are due to residual dynamics that makes the electric field around aluminum nuclei more symmetric. Thus, NMR spectroscopic signatures of 27 Al greatly vary with temperature; this information illustrates the importance of accounting for the temperature effect when confronting experimental and calculated C Q values of the corresponding aluminum sites in zeolites in order to obtain accurate structural assessment.