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Accessibility of Lithium Cations in VSH‐2 Zeotype: Structural Effects and Formation of Protonated Water Clusters

Danisi, Rosa Micaela 1; Fischer, Michael
1 Institut für Angewandte Geowissenschaften (AGW), Karlsruher Institut für Technologie (KIT)

Abstract:

The accessibility of lithium cations in microporous vanadosilicate VSH-2Cs of composition Cs2(VO)(Si6O14) ⋅ 3H2O was investigated by Single Crystal X-ray Diffraction, Attenuated Total Reflection Fourier Transformed Infrared Spectroscopy and Density Functional Theory calculations. The topological symmetry of VSH-2Cs is described in space group Cmca. After Li-ion exchange, the structure of VSH-2Li adopted monoclinic symmetry (space group C2/c) with a=17.011(2) Å, b=8.8533(11) Å, c=12.4934(16) Å, β=91.677(4)°, V=1880.7(4) Å3. The strong interactions between Li ions and oxygen-framework atoms drive the main deformation mechanism, which is based on cooperative rotation of SiO4 and VO5 units around their oxygen atoms that behave as hinges. Exchange of Cs+ by Li+ is incomplete and accompanied by the formation of protonated species to counterbalance the electrostatic charge. The incorporation of protons is mediated by the presence of water dimers in the structural channels. H2O molecules in VSH-2Li account not only as “space-fillers” after the removal of large Cs ions but also mediate proton transfer to compensate the negative charge of the host vanadosilicate framework.

Zugehörige Institution(en) am KIT Institut für Angewandte Geowissenschaften (AGW)
Publikationstyp Zeitschriftenaufsatz
Publikationsdatum 14.11.2023
Sprache Englisch
Identifikator ISSN: 1434-1948, 0009-2940, 0365-947X, 0365-9488, 0365-9496, 1099-0682, 1434-2421, 2749-2567
KITopen-ID: 1000162638
Erschienen in European Journal of Inorganic Chemistry
Verlag Wiley-VCH Verlag
Band 26
Heft 32
Vorab online veröffentlicht am 18.09.2023
Schlagwörter zeotype materials, lithium ion-exchange, phase transformation, protonated water clusters, materials chemistry
Nachgewiesen in Dimensions
Web of Science
OpenAlex
Scopus
Globale Ziele für nachhaltige Entwicklung Ziel 6 – Sauberes Wasser und Sanitär-Einrichtungen

Verlagsausgabe §
DOI: 10.5445/IR/1000162638
Veröffentlicht am 28.09.2023
Seitenaufrufe: 45
seit 28.09.2023
Downloads: 57
seit 03.10.2023
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