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Cited by 25Zeolite Catalysis and SynthesisMetal-Organic Frameworks: Synthesis and ApplicationsMembrane Separation and Gas Transport

Critical Role of Dynamic Flexibility in Ge‐Containing Zeolites: Impact on Diffusion

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Gutiérrez‐Sevillano, Juan José, Calero, Sofía, Hamad, Said, Grau‐Crespo, Ricardo, Rey, Fernando, Valencia, Susana, Palomino, Miguel, Balestra, Salvador R. G. +1 more·2016·Chemistry – A European Journal
DOI 10.1002/chem.201600983PMC PMC6680141
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Abstract

Incorporation of germanium in zeolites is well known to confer static flexibility to their framework, by stabilizing the formation of small rings. In this work, we show that the flexibility associated to Ge atoms in zeolites goes beyond this static effect, manifesting also a clear dynamic nature, in the sense that it leads to enhanced molecular diffusion. Our study combines experimental and theoretical methods providing evidence for this effect, which has not been described previously, as well as a rationalization for it, based on atomistic grounds. We have used both pure‐silica and silico‐germanate ITQ‐29 (LTA topology) zeolites as a case study. Based on our simulations, we identify the flexibility associated to the pore breathing‐like behavior induced by the Ge atoms, as the key factor leading to the enhanced diffusion observed experimentally in Ge‐containing zeolites.

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  • The preferential location and strong directing effect of Ge toward D4r-containing zeolites are attributed to the larger germanium atomic radius, which introduces framework flexibility and high tolerance to relatively acute T-O-T bond angles, resulting in zeolites having low framework densities.

    “The preferential location and strong directing effect toward D4r-containing zeolites have been attributed to the larger germanium atomic radius,72−74 which introduces framework flexibility and high tolerance in the crystal structure to relatively acute T–O–T bond angles resulting in zeolites having low framework densities as predicted by Brunner.75”

    From Zeolites in Adsorption Processes: State of the Art and Future Prospects (2022) · cites this paper as [74]

    Split into 2 atoms — 0 confirmed, 2 partially supported, 0 disputed, 0 misattributed, 0 unverifiable. Expand the claim to see per-atom verdicts.

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  • Zeolite framework flexibility is the underlying reason for close-fitting molecules being able to diffuse inside the pore system.

    “Zeolite framework flexibility is the underlying reason for close-fitting molecules being able to diffuse inside the pore system.”

    From Zeolites in Adsorption Processes: State of the Art and Future Prospects (2022) · cites this paper as [74]

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Authors
Gutiérrez‐Sevillano, J. J., Calero, S., Hamad, S., Grau‐Crespo, R., Rey, F., Valencia, S., Palomino, M., Balestra, S. R. G., & Ruiz‐Salvador, A. R.
Affiliations
  • Universidad Pablo de Olavide (ES)
  • Department Physical, Chemical and Natural Systems Univ. Pablo de Olavide Ctra. de Utrera km. 1 41013 Seville Spain
  • University of Reading (GB)
  • Consejo Superior de Investigaciones Científicas (ES)
Corresponding author
  • Rey, Fernando
  • Ruiz‐Salvador, A. Rabdel
ORCID
Venue
Chemistry – A European Journal
Publisher
Wiley
Published
2016-06-15
Volume
22
Issue
29
Pages
10036-10043
ISSN
  • 0947-6539 (ISSN-L)
  • 1521-3765
DOI
10.1002/chem.201600983
PMC
PMC6680141
OpenAlex
W2435630038
Cited by
25
References
61
Citations by year
2026: 1 · 2025: 2 · 2023: 3 · 2022: 2 · 2021: 4 · 2020: 1 · 2019: 2 · 2018: 4 · 2017: 5 · 2016: 1
FWCI
1.57
Type
journal article
Language
en
Open access
Licence
Locations
  • Chemistry - A European Journal (publishedVersion, cc-by-nc-nd)
  • Europe PMC (PubMed Central) (publishedVersion, cc-by-nc-nd)
  • PubMed Central (publishedVersion, cc-by-nc-nd)
  • PubMed (publishedVersion)
  • CentAUR (University of Reading) (submittedVersion)
  • RIO (Universidad Pablo de Olavide) (submittedVersion, cc-by-nc-nd)
  • RiuNet (Universitat Politècnica de València) (submittedVersion, cc-by-nc-nd)
Funders
European Research Council (ERC2011-StG-279520-RASPA)
Topics
  • Physical Sciences › Chemistry › Inorganic Chemistry › Zeolite Catalysis and Synthesis
  • Physical Sciences › Chemistry › Inorganic Chemistry › Metal-Organic Frameworks: Synthesis and Applications
  • Physical Sciences › Engineering › Mechanical Engineering › Membrane Separation and Gas Transport
Keywords
dynamic flexibility, molecular diffusion, atomistic simulation

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