Aluminium siting in the ZSM-5 framework by combination of high resolution Al NMR and DFT/MM calculationsw

The Al siting in the ZSM-5 zeolite was investigated by Al 3Q MAS NMR spectroscopy and QM/MM calculations. It was found that the occupation of the framework T-sites by Al and the concentration of Al in these T-sites are neither random nor controlled by a simple rule. They both depend on the conditions of the zeolite synthesis. At least 12 out of the 24 distinguishable framework T-sites of ZSM-5 are occupied by Al in the set of the investigated zeolite samples. A partial identification of the Al sites is possible. The calculated Al NMR shielding values were converted to Al isotropic chemical shifts using the experimental isotropic chemical shift of 60.0 ppm referenced to the aqueous solution of Al(NO3)3 and the corresponding calculated NMR shielding of 490.0 ppm of a silicon rich (Si/Al 38) chabazite structure zeolite as a secondary internal standard. The observed Al isotropic chemical shifts of 50.0 and 54.7 ppm correspond to Al atoms in the T20 and T6 sites, respectively. The pair of measured isotropic chemical shifts of 52.9 and 53.7 ppm can be assigned to the T4, T8 pair. At the low-shielding end, two assignments are plausible. The smallest deviations between the calculated and observed isotropic chemical shifts are reached for the assignment as follows: T24 (64.8 ppm) is not occupied in the samples and that the observed isotropic chemical shifts 63.6, 62.8, and 60.0 ppm belong to T1, T17, and T7, respectively. It follows then that T-sites T12 (60.8 ppm), T3 (61.7 ppm), and T18 (62.0 ppm) are most likely not occupied by Al in our ZSM-5 samples. If we assume that the calculated isotropic chemical shifts are systematically larger than the observed ones then we can assign the largest observed isotropic chemical shifts of 63.6 and 62.8 ppm to the least shielded T24 and T1 sites, respectively, and 60.0 ppm to T12. Then the sites T3 (61.7 ppm), T18 (62.0 ppm), and T17 (62.5 ppm) would be unoccupied by Al in our ZSM-5 samples. It was further shown that there is no simple linear relationship between the observed Al isotropic chemical shifts and the average Al–O–Si angles.