TY - JOUR
T1 - Sub-5 Ångstrom Porosity Tuning in Calixarene-Derived Porous Liquids via Supramolecular Complexation Construction
AU - Li, Errui
AU - Ganesan, Arvind
AU - Liu, Hongjun
AU - Ivanov, Alexander S.
AU - He, Lilin
AU - Nalaoh, Phattananawee
AU - Jenkins, David M.
AU - Steren, Carlos Alberto
AU - Mokhtari-Nori, Narges
AU - Hu, Jianzhi
AU - Li, Bo
AU - Jiang, De en
AU - Mahurin, Shannon M.
AU - Yang, Zhenzhen
AU - Dai, Sheng
N1 - Publisher Copyright:
© 2025 Wiley-VCH GmbH.
PY - 2025
Y1 - 2025
N2 - 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 CO2 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 CO2 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.
AB - 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 CO2 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 CO2 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.
KW - Calixarene
KW - Carbon dioxide
KW - Molecular sieving effect
KW - Porous liquid
KW - Supramolecular complexation
UR - http://www.scopus.com/inward/record.url?scp=85214991053&partnerID=8YFLogxK
U2 - 10.1002/anie.202421615
DO - 10.1002/anie.202421615
M3 - Article
AN - SCOPUS:85214991053
SN - 1433-7851
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
ER -