Cited by 136Zeolite Catalysis and SynthesisCarbon Dioxide Capture TechnologiesMetal-Organic Frameworks: Synthesis and Applications

Cation Gating and Relocation during the Highly Selective “Trapdoor” Adsorption of CO 2 on Univalent Cation Forms of Zeolite Rho

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Lozinska, Magdalena M., Mowat, John P. S., Wright, Paul A., Thompson, Stephen P., Jorda, Jose L., Palomino, Miguel, Valencia, Susana, Rey, Fernando·2014·Chemistry of Materials

Abstract

Adsorption of CO 2 and CH 4 has been measured on the Na-, K-, and Cs-forms of zeolite Rho (0–9 bar; 283–333 K). Although CH 4 is excluded, CO 2 is readily taken up, although the uptake at low pressures decreases strongly, in the order Na + > K + > Cs + . Structural studies by powder X-ray diffraction (PXRD) suggest that cations in intercage window sites block CH 4 adsorption; however, in the presence of CO 2, the cations can move enough to permit adsorption (several angstroms). Determination of time-averaged cation positions during CO 2 adsorption at 298 K by Rietveld refinement against PXRD data shows that (i) in Na-Rho, there is a small relaxation of Na + cations within single eight-ring (S8R) sites, (ii) in Cs-Rho, D8R cations move to S8R sites (remaining within windows) and two phases of Cs-Rho ( I 4̅3 m, Im 3̅ m ) are present over a wide pressure range, and (iii) in K-Rho, there is relocation of some K + cations from window sites to cage sites and two phases coexist, each with I 4̅3 m symmetry, over the pressure range of 0–1 bar. The final cation distributions at high P CO 2 are similar for Na-, K-, and Cs-Rho, and adsorption in each case is only possible by “trapdoor”-type cation gating. Complementary studies on K-chabazite (Si/Al = 3) also show changes in time-averaged cation location during CO 2 adsorption.

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Crossref · 10.1021/cm404028f

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  • CO2 adsorption on RHO and related zeolites involves simultaneous cation relocation and structure change.

    “Another interesting case, in which cation relocation and structure change take place simultaneously, is that of CO2 adsorption on RHO and related zeolites.”
  • In RHO and RHO-related structures, selectivity is enhanced by structural changes in framework and cation relocation upon CO2 adsorption; these changes and trapdoor effects do not take place upon CH4 adsorption, leading to extremely high selectivities.

    “In the case of RHO and RHO-related structures, the selectivity is enhanced by structural changes in the framework and in cation relocation upon CO2 adsorption.261,263,273−275,502,512−515 These structural changes and trapdoor effects do not take place upon CH4 adsorption, which leads to extremely high selectivities.”

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Authors
Lozinska, M. M., Mowat, J. P. S., Wright, P. A., Thompson, S. P., Jorda, J. L., Palomino, M., Valencia, S., & Rey, F.
Affiliations
  • EaStCHEM School of Chemistry, University of St. Andrews, Purdie Building, North Haugh, St. Andrews, Fife KY16 9ST, Scotland
  • University of St Andrews (GB)
  • Diamond Light Source (GB)
  • Instituto de Tecnología Química (UPV-CSIC), Universidad Politécnica de Valencia, Consejo Superior de Investigaciones Científicas, Avenida de los Naranjos s/n, 46022 Valencia, Spain
  • Consejo Superior de Investigaciones Científicas (ES)
Corresponding author
Wright, Paul A.
Venue
Chemistry of Materials
Published
2014-03-06
Volume
26
Issue
6
Pages
2052-2061
ISSN
  • 0897-4756 (ISSN-L)
  • 1520-5002
OpenAlex
W2316580653
Cited by
135
References
27
Citations by year
2026: 12 · 2025: 19 · 2024: 15 · 2023: 13 · 2022: 11 · 2021: 12 · 2020: 7 · 2019: 7 · 2018: 12 · 2017: 8 · 2016: 8 · 2015: 8 · 2014: 3
FWCI
3.84
Type
journal article
Language
en
Open access
Licence
cc-by-nc-nd
Locations
  • Chemistry of Materials (publishedVersion)
  • RiuNet (Universitat Politècnica de València) (submittedVersion, cc-by-nc-nd)
Funders
Engineering and Physical Sciences Research Council (EP/G062129/1, EP/J02077X/1)
Topics
  • Physical Sciences › Chemistry › Inorganic Chemistry › Zeolite Catalysis and Synthesis
  • Physical Sciences › Engineering › Mechanical Engineering › Carbon Dioxide Capture Technologies
  • Physical Sciences › Chemistry › Inorganic Chemistry › Metal-Organic Frameworks: Synthesis and Applications
Keywords
CO2 adsorption, RHO zeolite, CH4 adsorption

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