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Quantitatively Probing the Al Distribution in Zeolites

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journal contribution
posted on 11.06.2014, 00:00 by Aleksei Vjunov, John L. Fulton, Thomas Huthwelker, Sonia Pin, Donghai Mei, Gregory K. Schenter, Niranjan Govind, Donald M. Camaioni, Jian Zhi Hu, Johannes A. Lercher
The degree of substitution of Si4+ by Al3+ in the oxygen-terminated tetrahedra (Al T-sites) of zeolites determines the concentration of ion-exchange and Brønsted acid sites. Because the location of the tetrahedra and the associated subtle variations in bond angles influence the acid strength, quantitative information about Al T-sites in the framework is critical to rationalize catalytic properties and to design new catalysts. A quantitative analysis is reported that uses a combination of extended X-ray absorption fine structure (EXAFS) analysis and 27Al MAS NMR spectroscopy supported by DFT-based molecular dynamics simulations. To discriminate individual Al atoms, sets of ab initio EXAFS spectra for various T-sites are generated from DFT-based molecular dynamics simulations, allowing quantitative treatment of the EXAFS single- and multiple-photoelectron scattering processes out to 3–4 atom shells surrounding the Al absorption center. It is observed that identical zeolite types show dramatically different Al distributions. A preference of Al for T-sites that are part of one or more 4-member rings in the framework over those T-sites that are part of only 5- and 6-member rings in an HBEA150 zeolite has been determined using this analysis.