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Open AccessArticle

DFT Study of Si/Al Ratio and Confinement Effects on the Energetics and Vibrational Properties of some Aza-Aromatic Molecules Adsorbed on H-ZSM-5 Zeolite

1
Laboratoire de Chimie Théorique, UMR 7616 CNRS, Sorbonne Université, 4 place Jussieu, 75252 Paris, France
2
Laboratoire de Spectrochimie Infrarouge et Raman, UMR 8516 CNRS, Université Lille, 59650 Villeneuve d’Ascq, France
*
Author to whom correspondence should be addressed.
Computation 2020, 8(3), 81; https://doi.org/10.3390/computation8030081
Received: 4 July 2020 / Revised: 4 September 2020 / Accepted: 8 September 2020 / Published: 10 September 2020
(This article belongs to the Special Issue New Advances in Density Functional Theory and Its Application)
The Si/Al ratio and confinement effects of zeolite framework on energetics and vibrational frequencies of pyridine and 4,4′-bipyridine adsorbed on Brønsted acid sites in the straight channel of H-ZSM-5 are investigated by DFT calculations at the B3LYP and M06-2X+D3 levels. The straight channel of H-ZSM-5 is simulated by a cluster of 32 tetrahedral centers covering the intersection between straight and zigzag channels. Pyridine and 4,4′-bipyridine adsorption at two different sites in the intersection (open region) and/or in the narrow region situated between two intersections (closed region) is studied. For two Si/Al ratios (31, 15), the ion pair complexes formed by proton transfer upon pyridine and 4,4′-bipyridine adsorption in the open region and for the first time in the closed region are characterized. Our results indicate: (i) the stability for all adsorption complexes is essentially governed by the dispersive van der Waals interactions and the open region is energetically more favorable than the closed region owing to the predominance of the dispersive interactions over the steric constraints exerted by the confinement effects; (ii) as the Al centers are sufficiently spaced apart, Si/Al ratio does not influence pyridine adsorption energy, but significantly affects the adsorption energies and the relative stability of 4,4′-bipyridine complexes; (iii) neither Si/Al ratio nor confinement significantly influence pyridine and 4,4′-bipyridine vibrational frequencies within their complexes. View Full-Text
Keywords: H-ZSM-5 zeolite; aza-aromatics; proton transfer; Si/Al ratio effect; confinement effect; DFT-D calculations H-ZSM-5 zeolite; aza-aromatics; proton transfer; Si/Al ratio effect; confinement effect; DFT-D calculations
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Castellà-Ventura, M.; Moissette, A.; Kassab, E. DFT Study of Si/Al Ratio and Confinement Effects on the Energetics and Vibrational Properties of some Aza-Aromatic Molecules Adsorbed on H-ZSM-5 Zeolite. Computation 2020, 8, 81.

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