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Title: Quantitatively Probing the Al Distribution in Zeolites

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. As 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 the HBEA150 sample has been determined from a combination of these methods. This work was supported by the U. S. Department of Energy (DOE), Office ofmore » Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences.« less
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Publication Date:
OSTI Identifier:
Report Number(s):
47841; KC0302010
DOE Contract Number:
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society, 136(23):8296-8306
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org:
Country of Publication:
United States
aluminum; extended X-ray absorption fine structure spectroscopy; MD-EXAFS; HBEA structure; zeolite T-sites; Environmental Molecular Sciences Laboratory