Two Kinds of Framework Al Sites Studied in BEA Zeolite by X-ray Diffraction, Fourier Transform Infrared Spectroscopy, NMR Techniques, and V Probe

Abstract

The dealumination of BEA zeolite by treatment with concentrated nitric acid is evidenced by X-ray diffraction (XRD) and Fourier Transform Infrared (FTIR) spectroscopy. Two-dimensional 27Al 3Q and 5Q magic-angle-spinning (MAS) NMR allow the detection of two kinds of tetrahedral Al atoms whose relative amounts depend on the Si/Al ratio and which correspond to two specific T-sites. 29Si MAS NMR and 1H MAS NMR measurements confirm these results. 29Si MAS NMR spectra evidence two resonances at around −114 and −111 ppm ascribed to Si sites of the Si(OSi)4 environment of two different crystallographic sites. Moreover, the presence of Si atoms associated with hydroxyl groups is confirmed by a resonance at −102 ppm when 1H−29Si CP is applied. The Bronsted and Lewis acidic sites in dealuminated BEA zeolites are evidenced by FTIR spectra of adsorbed pyridine which show two kinds of bridging hydroxyl groups (Si−O(H)−Al) of different acid strength. 51V MAS NMR confirms the incorporation of vanadium atoms into vacant T...