Active Sites in H-Mordenite Catalysts Probed by NMR and FTIR

Abstract

Mordenites are widely used in catalysis and environmental protection. The catalytic properties of mordenite are largely determined by the composition of its crystal framework, i.e., the SiO2/Al2O3 molar ratio (MR), and the cationic form. In H-mordenites, the most important characteristic becomes the structure and distribution of acid sites, which depends on the number and distribution of Al tetrahedra in the framework. In the present work, the local structure of these centers in H-mordenite catalysts with a nominal MR varied from 9.9 to 19.8 was studied in detail using a combination of magic angle spinning nuclear magnetic resonance (MAS NMR) and Fourier transform infrared spectroscopy (FTIR). 27Al MAS NMR indicates the presence of extra-framework Al in most of the studied samples that results in a higher real MR of the zeolitic framework compared to the nominal value. Concentrations of Lewis and Brønsted acid sites, as well as of silanol groups were estimated by elemental analysis, NMR, and FTIR spectroscopy. The values of site concentrations obtained from band intensities of adsorbed CO and those of OH groups are compared with the amount of framework and extra-framework aluminum. The advantages and restrictions of different methods of active site characterization are discussed.