Abstract
Zeolites are three-dimensional, crystalline silicate-based materials of interest for catalysis and separations. Computational models of zeolites must capture their three-dimensional structure, the intrinsic microscopic heterogeneity introduced by heteroatom substitutions that underlie their interesting chemical behavior, and the dynamic nature of reactive sites within the pores of molecular dimensions. Here we describe the use of supercell density functional theory (DFT) models for tackling these problems, focusing primarily on Brønsted acidic and Cu-exchanged chabazite (CHA) zeolites and their chemistry related to the catalytic chemistry of nitrogen oxides ( NOx). We describe considerations important in model construction, applications of ab initio molecular dynamics to structure annealing and accurate computations of reaction and activation free energies, first-principles thermodynamics approaches for predicting site compositions at realistic conditions, and approaches for incorporating heteroatom distributions into material models.
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Acknowledgements
This work was prepared in part with the financial support of the BASF Corporation. Numerous valuable discussions with C. Paolucci, H. Li, A. DeBellis, and I. Müller are gratefully acknowledged.
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Li, S., Schneider, W.F. (2018). Supercell Models of Brønsted and Lewis Sites in Zeolites. In: Andreoni, W., Yip, S. (eds) Handbook of Materials Modeling. Springer, Cham. https://doi.org/10.1007/978-3-319-50257-1_4-1
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DOI: https://doi.org/10.1007/978-3-319-50257-1_4-1
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