Hiding extra-framework cations in zeolites L and Y by internal ion exchange and its effect on CO2 adsorption
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The fully La-exchanged form of the large pore zeolite L, La3.0Al9.0Si27.0O72, has been prepared by repeated aqueous ion exchange and internal cation exchange resulting from calcination to give a low silica zeolite (Si/Al = 3) with all cations hidden from available porosity. This results from the migration of La3+ from sites in the large 12-membered ring (12R) channel (exchangeable via aqueous solution) to ‘closed’ sites in the structure. The mechanism for this internal cation exchange, which has been elucidated by Rietveld analysis of powder X-ray diffraction data, comprises sequential La3+ migration, first to ste cages between cancrinite (can) cages in the framework and then into the can cages. In each case K+ cations must first leave the closed cages, in the first case through 8Rs, in the second via puckered 6Rs. The first migration step is achieved by 573 K, the second by 1073 K. Decrease of the K+ occupation in accessible main channel sites of zeolites K9.0-, K5.7La1.1-, K2.7La2.1- and La3.0-L strongly changes the shape of the CO2 adsorption isotherms, as the strength of interaction decreases. The Henry Law constant for K9.0-L zeolite is 36.60(2) mol (kg bar)-1, whereas for La3.0-L it is 1.80(3) mol (kg bar)-1, if an initial uptake of 0.1 mmol g-1 is neglected. The isosteric heat of adsorption is correspondingly strongly reduced. A CO2 isotherm shape similar to that observed for La-L is also shown by a fully-exchanged La-Y, La18.7Al56.0Si136.0O384, prepared from Na-Y by repeated aqueous and internal ion exchange. In this case the internal exchange requires the egress of Na+ cations from sodalite cages via planar 6R windows and so is possible at lower temperatures (<673 K). The ability to modify CO2 isotherm shape in low silica zeolites by hiding cations in inaccessible cages can be of interest to tailor pressure swing adsorbents for a range of CO2-containing gas streams.
Lozinska , M M , Miller , D N , Brandani , S & Wright , P A 2020 , ' Hiding extra-framework cations in zeolites L and Y by internal ion exchange and its effect on CO 2 adsorption ' , Journal of Materials Chemistry A , vol. Advance Article . https://doi.org/10.1039/C9TA09783J
Journal of Materials Chemistry A
Copyright © 2020 The Author(s). This work has been made available online in accordance with publisher policies or with permission. Permission for further reuse of this content should be sought from the publisher or the rights holder. This is the author created accepted manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1039/C9TA09783J
DescriptionThe authors gratefully acknowledge the EPSRC (FLEXICCS – Flexible Industrial Carbon Capture, EPSRC EP/N024613/1 (MML, SB and PAW) and Capital for Great Technologies, EP/L017008/1 (DNM)) for funding. The research data underpinning this publication can be accessed at https://doi.org/10.17630/1fff8eca-c51d-4c6e-a8a9-0ec83939479c
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