Retarded O2 transport in Co2+-coordinated supramolecular polymer networks for membrane CO2/O2 separations†
Abstract
Dissociated Co2+ ions in liquids and polymers have been demonstrated to reversibly react with O2 and increase O2 permeability. However, we find a series of Co2+-coordinated supramolecular polymer networks (SPNs) with enormous O2 sorption but retarded diffusion, leading to superior CO2/O2 separation properties. Specifically, Co(BF4)2 is dissolved by cross-linked poly(ethylene oxide) (XLPEO), as validated by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and differential scanning calorimetry (DSC). The dissociated Co2+ ions increase O2/CO2 solubility selectivity but decrease its diffusivity selectivity. For example, adding 6.4 mass% Co(BF4)2 in XLPEO increases O2 solubility by 35 times and O2/CO2 solubility selectivity from 0.12 to 5.0, but it decreases O2/CO2 diffusivity selectivity from 0.40 to 0.0058, leading to a CO2/O2 permeability selectivity of 35, above Robeson's upper bound and superior to that of state-of-the-art polymers. This study unravels an exciting platform of metal ion-coordinated supramolecular networks for various molecular separations by harnessing strong affinity but retarded diffusion despite their stability challenge.