Sub‐5 Ångstrom Porosity Tuning in Calixarene‐Derived Porous Liquids via Supramolecular Complexation Construction

Li, Errui; Ganesan, Arvind; Liu, Hongjun; Ivanov, Alexander S.; He, Lilin; Nalaoh, Phattananawee; Jenkins, David M.; Steren, Carlos Alberto; Mokhtari‐Nori, Narges; Hu, Jianzhi; Li, Bo; Jiang, De‐en; Mahurin, Shannon M.; Yang, Zhenzhen; Dai, Sheng

doi:10.1002/ange.202421615

Title: Sub‐5 Ångstrom Porosity Tuning in Calixarene‐Derived Porous Liquids via Supramolecular Complexation Construction

Journal Article · Thu Jan 16 00:00:00 UTC 2025 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202421615 · OSTI ID:2530692

Li, Errui ^[1]; Ganesan, Arvind ^[2]; Liu, Hongjun ^[3]; Ivanov, Alexander S. ^[2]; He, Lilin ^[4]; Nalaoh, Phattananawee ^[1]; Jenkins, David M. ^[1]; Steren, Carlos Alberto ^[1]; Mokhtari‐Nori, Narges ^[1]; Hu, Jianzhi ^[5]; Li, Bo ^[3]; Jiang, De‐en ^[3]; Mahurin, Shannon M. ^[2];

^[2]; Dai, Sheng ^[6]

Department of Chemistry University of Tennessee Knoxville Knoxville TN 37996 USA
Chemical Sciences Division Oak Ridge National Laboratory Oak Ridge TN 37831 USA
Department of Chemical and Biomolecular Engineering Vanderbilt University Nashville TN 37235 USA
Neutron Scattering Division Oak Ridge National Laboratory Oak Ridge TN 37831 USA
Pacific Northwest National Laboratory Richland WA 99352 USA, The Gene &, Linda Voiland School of Chemical Engineering and Bioengineering Washington State University Pullman WA 99164 USA
Department of Chemistry University of Tennessee Knoxville Knoxville TN 37996 USA, Chemical Sciences Division Oak Ridge National Laboratory Oak Ridge TN 37831 USA

Abstract Sub‐Ångstrom‐level porosity engineering, which is appealing in gas separations, has been demonstrated in solid carbon, polymer, and framework materials but rarely achieved in the liquid phase. In this work, a gas molecular sieving effect in the liquid phase at sub‐5 Ångstrom scale is created via sophisticated porosity tuning in calixarene‐derived porous liquids (PLs). Type II PLs are constructed via supramolecular complexation between the sodium salts of calixarene derivatives and crown ether solvents. The chemical structure variation and assembly behavior of the porous host upon PL construction are monitored by spectroscopy‐, X‐ray‐, and neutron‐scattering techniques. The presence of permanent porosity in calixarene‐derived PLs is verified by pressure swing gas uptake, altered CO ₂ physisorption behavior, and molecular simulations. Sub‐5 Ångstrom porosity tuning within the PL phase is achieved by introducing bulky substituted groups on the benzene ring of the calixarene host, which then greatly affects the dynamic motion and transport behavior of CO ₂ molecules and the Xe uptake performance. The approach being demonstrated in this work represents a promising pathway to tune and leverage the porosity effect for enhanced gas uptake capacity and selectivity in liquid sorbents.

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Sponsoring Organization:: USDOE

OSTI ID:: 2530692

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 11 Vol. 137; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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