Distribution of Aluminum over the Tetrahedral Sites in ZSM-5 Zeolites and Their Evolution after Steam Treatment

Zeolite ZSM-5 is one of the most widely used zeolites, in particular in heterogeneous catalysis. This work investigates the incorporation of Al in the silica framework of monoclinic ZSM-5 and the Al speciation during steam treatment for four ZSM-5 samples with different Si/Al ratios, using ultrahigh field Al-27 NMR (22.3 T), Si-29 NMR, X-ray diffraction, and IR spectroscopy. Al-27 MQMAS NMR at 22.3 T allows identification and quantification of 10 distinct tetrahedral framework resonances which are assigned to the crystallographic sites by their average T-O-T angles, determined from powder XRD patterns for the same samples. A clear Al site preference is observed and found to be dependent on the Si/Al ratio of the parent zeolite. The framework sites facing the intersections in ZSM-S are found to be most prone to dealumination, whereas Al in the straight and sinusoidal-shaped channels are more stable toward steam treatment at high temperatures. Extra-framework Al species with 5- and 6-fold coordination and two distorted tetrahedral AlO4 sites have also been identified. The spectroscopic data are supported by catalytic activities from a-test cracking experiments which are in accordance with a reinsertion of Al in the framework at mild steaming and the onset of dealumination at higher temperatures.