Thermodynamic analysis of framework deformation in Na,Cs-RHO zeolite upon CO 2 adsorption
Open accessAbstract
Fully dehydrated and partially sodium-cesium containing RHO zeolite (Na,Cs-RHO) shows a genuine inflection in the CO2 isotherms in the temperature range 293-333 K that can be attributed to a sorbate-induced framework deformation from an acentric (A) to a centric (C) phase due to a partial cation rearrangement. This peculiar sorption pattern can be captured by the formulation of thermodynamic isotherms, providing a direct enthalpic and entropic signature of the CO2 adsorption-desorption process during deformation. Using this formulation, the energy barrier between the acentric and centric phases for CO2 adsorption-desorption was estimated in the range 4.7-9.6 J g(-1) of solid (15-32 kJ mol(-1)), reflecting a higher CO2 affinity for the acentric phase, whereas the elastic energy involved during framework distortion was estimated in the range 6-12 J g(-1) of solid (19-39 kJ mol(-1)) with a relative maximum at 303 K and showing a dominant entropic contribution.
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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.”
From Zeolites in Adsorption Processes: State of the Art and Future Prospects (2022) · cites this paper as [274]
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.”
From Zeolites in Adsorption Processes: State of the Art and Future Prospects (2022) · cites this paper as [274]
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Palomino, M., Corma, A., Jordá, J. L., Rey, F., & Valencia, S. (2012) · Chem. Commun. · doi:10.1039/c1cc16320e · Cited by 161 · see citing works
Self-citationLozinska, M. M., Mowat, J. P. S., Wright, P. A., Thompson, S. P., Jorda, J. L., Palomino, M., Valencia, S., & Rey, F. (2014) · Chemistry of Materials · doi:10.1021/cm404028f · Cited by 135 · see citing works
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Zeolites in Adsorption Processes: State of the Art and Future Prospects
Pérez-Botella, E., Valencia, S., & Rey, F. (2022) · Chemical Reviews · doi:10.1021/acs.chemrev.2c00140 · Cited by 1,126 · see citing works
Self-citationPérez-Botella, E., Palomino, M., Valencia, S., & Rey, F. (2019) · Green Energy and Technology · doi:10.1007/978-981-13-3504-4_7 · Cited by 29 · see citing works
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- Authors
- Pera-Titus, M., Palomino, M., Valencia, S., & Rey, F.
- Affiliations
- Consejo Superior de Investigaciones Científicas (ES)
- Venue
- Phys. Chem. Chem. Phys.
- Publisher
- Royal Society of Chemistry (RSC)
- Published
- 2014-09-30
- Volume
- 16
- Issue
- 44
- Pages
- 24391-24400
- ISSN
- 1463-9076 (ISSN-L)
- 1463-9084
- OpenAlex
- W2114674049
- Cited by
- 22
- References
- 2
- Citations by year
- 2025: 1 · 2023: 5 · 2022: 4 · 2021: 1 · 2020: 1 · 2019: 4 · 2018: 3 · 2016: 3
- FWCI
- 0.43
- Type
- journal article
- Language
- en
- Open access
- green
- hdl.handle.net
- Licence
- cc-by-nc-nd
- Locations
- Physical Chemistry Chemical Physics (publishedVersion)
- PubMed (publishedVersion)
- ORCA Online Research @Cardiff (Cardiff University) (submittedVersion)
- RiuNet (Universitat Politècnica de València) (submittedVersion, cc-by-nc-nd)
- Topics
- Physical Sciences › Chemistry › Inorganic Chemistry › Zeolite Catalysis and Synthesis
- Physical Sciences › Engineering › Mechanical Engineering › Carbon Dioxide Capture Technologies
- Physical Sciences › Chemistry › Spectroscopy › Adsorption, diffusion, and thermodynamic properties of materials
- Keywords
- RHO zeolite, CO2 adsorption, framework deformation, cationic rearrangement, sorption isotherms, enthalpy and entropy of adsorption, energy barrier, elastic energy, CO2 affinity
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