Carbon Capture Membranes Based on Amorphous Polyether Nanofilms Enabled by Thickness Confinement and Interfacial Engineering

Thin-film composite membranes are a leading technology for post-combustion carbon capture, and the key challenge is to fabricate defect-free selective nanofilms as thin as possible (100 nm or below) with superior CO₂/N₂ separation performance. Herein, we developed high-performance membranes based on an unusual choice of semi-crystalline blends of amorphous poly(ethylene oxide) (aPEO) and 18-crown-6 (C6) using two nanoengineering strategies. First, the crystallinity of the nanofilms decreases with decreasing thickness and completely disappears at 500 nm or below because of the thickness confinement. Second, polydimethylsiloxane is chosen as the gutter layer between the porous support and selective layer, and its surface is modified with bio-adhesive polydopamine (<10 nm) with an affinity toward aPEO, enabling the formation of the thin, defect-free, amorphous aPEO/C6 layer. For example, a 110 nm film containing 40 mass % C6 in aPEO exhibits CO₂ permeability of 900 Barrer (much higher than a thick film with 420 Barrer), rendering a membrane with a CO₂ permeance of 2200 GPU and CO₂/N₂ selectivity of 27 at 35 °C, surpassing Robeson’s upper bound. This work shows that engineering at the nanoscale plays an important role in designing high-performance membranes for practical separations.