Understanding carbon dioxide adsorption on univalent cation forms of the flexible zeolite Rho at conditions relevant to carbon capture from flue gases

Magdalene Lozinska, Enzo Mangano, John Mowat, Ashley Marie Shepherd, Russell Francis Howe, Stephen Thompson, Julia Parker, Stefan Brandani, Paul Wright

Research output: Contribution to journalArticle

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Abstract

series of univalent cation forms of zeolite Rho (M(9.8)Al(9.8)Si(38.2)O(96), M = H, Li, Na, K, NH(4), Cs) and ultrastabilized zeolite Rho (US-Rho) have been prepared. Their CO(2) adsorption behavior has been measured at 298 K and up to 1 bar and related to the structures of the dehydrated forms determined by Rietveld refinement and, for H-Rho and US-Rho, by solid state NMR. Additionally, CO(2) adsorption properties of the H-form of the silicoalumino-phosphate with the RHO topology and univalent cation forms of the zeolite ZK-5 were measured for comparison. The highest uptakes at 0.1 bar, 298 K for both Rho and ZK-5 were obtained on the Li-forms (Li-Rho, 3.4 mmol g(-1); Li-ZK-5, 4.7 mmol g(-1)). H- and US-Rho had relatively low uptakes under these conditions: extra-framework Al species do not interact strongly with CO(2). Forms of zeolite Rho in which cations occupy window sites between a-cages show hysteresis in their CO(2) isotherms, the magnitude of which (Na(+),NH(4)(+) < K(+) < Cs(+)) correlates with the tendency for cations to occupy double eight-membered ring sites rather than single eight-membered ring sites. Hysteresis is not observed for zeolites where cations do not occupy the intercage windows. In situ synchrotron X-ray diffraction of the CO(2) adsorption on Na-Rho at 298 K identifies the adsorption sites. The framework structure of Na-Rho "breathes" as CO(2) is adsorbed and desorbed and its desorption kinetics from Na-Rho at 308 K have been quantified by the Zero Length Column chromatographic technique. Na-Rho shows much higher CO(2)/C(2)H(6) selectivity than Na-ZK-5, as determined by single component adsorption, indicating that whereas CO(2) can diffuse readily through windows containing Na(+) cations, ethane cannot.

Original languageEnglish
Pages (from-to)17628-17642
Number of pages15
JournalJournal of the American Chemical Society
Volume134
Issue number42
Early online date26 Sep 2012
DOIs
Publication statusPublished - 24 Oct 2012

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Zeolites
Carbon capture
Carbon Monoxide
Flue gases
Carbon Dioxide
Adsorption
Cations
Carbon dioxide
Carbon
Gases
Positive ions
Hysteresis
Rietveld refinement
Ethane
Synchrotrons
Isotherms
Desorption
Phosphates
Least-Squares Analysis
Nuclear magnetic resonance

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Understanding carbon dioxide adsorption on univalent cation forms of the flexible zeolite Rho at conditions relevant to carbon capture from flue gases. / Lozinska, Magdalene; Mangano, Enzo; Mowat, John; Shepherd, Ashley Marie; Howe, Russell Francis; Thompson, Stephen; Parker, Julia; Brandani, Stefan; Wright, Paul.

In: Journal of the American Chemical Society, Vol. 134, No. 42, 24.10.2012, p. 17628-17642.

Research output: Contribution to journalArticle

Lozinska, Magdalene ; Mangano, Enzo ; Mowat, John ; Shepherd, Ashley Marie ; Howe, Russell Francis ; Thompson, Stephen ; Parker, Julia ; Brandani, Stefan ; Wright, Paul. / Understanding carbon dioxide adsorption on univalent cation forms of the flexible zeolite Rho at conditions relevant to carbon capture from flue gases. In: Journal of the American Chemical Society. 2012 ; Vol. 134, No. 42. pp. 17628-17642.
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AU - Shepherd, Ashley Marie

AU - Howe, Russell Francis

AU - Thompson, Stephen

AU - Parker, Julia

AU - Brandani, Stefan

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