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 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.
| Original language | English |
|---|---|
| Article number | e202421615 |
| Journal | Angewandte Chemie - International Edition |
| Volume | 64 |
| Issue number | 11 |
| DOIs | |
| State | Published - Mar 10 2025 |
Funding
The research was supported financially by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, US Department of Energy. 23Na 1D magic-angle spinning NMR experiments were supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences within the Catalysis Science Program (FWP 47319). SAXS and WAXS measurements were enabled by the Major Research Instrumentation program of the National Science Foundation under Award No. DMR-1827474. The X-ray PDF research used beamline 28-ID-1 (PDF) of the National Synchrotron Light Source II, a DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract No. DE-SC0012704. This research used resources at the High Flux Isotope Reactor, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory (IPTS-33565 and 32388). The research was supported financially by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, US Department of Energy. Na 1D magic‐angle spinning NMR experiments were supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences within the Catalysis Science Program (FWP 47319). SAXS and WAXS measurements were enabled by the Major Research Instrumentation program of the National Science Foundation under Award No. DMR‐1827474. The X‐ray PDF research used beamline 28‐ID‐1 (PDF) of the National Synchrotron Light Source II, a DOE Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under contract No. DE‐SC0012704. This research used resources at the High Flux Isotope Reactor, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory (IPTS‐33565 and 32388).
Keywords
- Calixarene
- Carbon dioxide
- Molecular sieving effect
- Porous liquid
- Supramolecular complexation