Regioselectivity of Al–O Bond Hydrolysis during Zeolites Dealumination Unified by Brønsted–Evans–Polanyi Relationship
Abstract
We determine the mechanism of the initiation of Al–O(H) bond breaking for zeolitic structures mordenite (MOR), faujasite (FAU), MFI, and chabazite (CHA) with high Si/Al ratio occurring during dealumination. Periodic density functional theory calculations demonstrate that water adsorption on the Al atom takes place in anti position to the Brønsted acid site, via a penta- or tetra-coordinated Al species. A subsequent 1,2-dissociation of water on adjacent framework oxygen atoms leads to the first Al–O(H) bond breaking (with activation energies of ∼76–125 kJ/mol). A Brønsted–Evans–Polanyi relationship to estimate transition states (TS) is established and opens the door to predictions of which crystallographic sites are able to initiate dealumination.
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Proper mechanistic understanding of BAS-water-zeolite interactions is still lacking, limited to either static calculations at ultra-high vacuum conditions or exploratory (ab initio) dynamical simulations of narrow scope.
“As a result, the proper mechanistic understanding of BAS-water-zeolite interactions is still lacking, limited to either static calculations at ultra-high vacuum conditions13,14 or exploratory (ab initio) dynamical simulations of narrow scope15–18.”
From A reactive neural network framework for water-loaded acidic zeolites (2024) · cites this paper as [13]
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Tailored Approach for Hierarchization of All-Silica ZeolitesPreprint
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- Authors
- Silaghi, M.-C., Chizallet, C., Petracovschi, E., Kerber, T., Sauer, J., & Raybaud, P.
- Affiliations
- IFP Énergies nouvelles (FR)
- Humboldt-Universität zu Berlin (DE)
- Corresponding author
- Raybaud, Pascal
- Venue
- ACS Catalysis
- Publisher
- American Chemical Society (ACS)
- Published
- 2014-11-24
- Volume
- 5
- Issue
- 1
- Pages
- 11-15
- ISSN
- 2155-5435 (ISSN-L)
- OpenAlex
- W2314439365
- Cited by
- 108
- References
- 39
- Citations by year
- 2026: 15 · 2025: 8 · 2024: 18 · 2023: 4 · 2022: 4 · 2021: 13 · 2020: 12 · 2019: 15 · 2018: 6 · 2017: 3 · 2016: 4 · 2015: 6
- FWCI
- 1.84
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- ACS Catalysis (publishedVersion)
- Funders
- Deutsche Forschungsgemeinschaft (CRC1109)
- IFP Energies Nouvelles
- Topics
- Physical Sciences › Chemistry › Inorganic Chemistry › Zeolite Catalysis and Synthesis
- Physical Sciences › Chemical Engineering › Catalysis › Catalysis and Oxidation Reactions
- Physical Sciences › Environmental Science › Waste Management and Disposal › Chemical Synthesis and Characterization
- Keywords
- regioselectivity, Brønsted–Evans–Polanyi relationship, transition state, Brønsted acid sites, mordenite, faujasite, MFI, chabazite, activation energy
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