Cited by 108Zeolite Catalysis and SynthesisCatalysis and Oxidation ReactionsChemical Synthesis and Characterization

Regioselectivity of Al–O Bond Hydrolysis during Zeolites Dealumination Unified by Brønsted–Evans–Polanyi Relationship

Silaghi, Marius-Christian, Chizallet, Céline, Petracovschi, Elena, Kerber, Torsten, Sauer, Joachim, Raybaud, Pascal·2015·ACS Catalysis

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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Crossref · 10.1021/cs501474u

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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.”

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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
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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