Stabilizing Ion Channels via Nonpolar Cross-Linking in Ion-Conductive Polymers for Robust CO₂-to-Alcohol Conversion

Efficient alcohol electrosynthesis from CO₂ relies on ion-conductive polymers to mediate ion transport and maintain product separation. However, alcohol-induced instability of ion channels within these polymers compromises electrolysis durability. Here we report a nonpolar cross-linked polymer architecture that stabilizes ion channels in alcohol-rich environments, enabling robust CO₂-to-alcohol conversion. Covalent integration of ion-conductive poly(arylene) piperidinium into a nonpolar poly(styrene) network creates a hydrophobic scaffold that confines ion channels, locking them against alcohol-induced swelling. The resulting structure retains over 97% of mechanical integrity after 1000 h of alcohol exposure, dramatically outperforming conventional poly(arylene) piperidinium that retains only 17% within 1 h. This excellent structural stability minimizes alcohol crossover and maintains efficient ion transport during electrolysis, sustaining continuous ethanol production with over 99% product retention and stable cell performance, whereas poly(arylene) piperidinium exhibits rapid failure. This work establishes nonpolar cross-linking as a general strategy for constructing stable ion channels within ion-conductive polymers, offering a molecular design approach for durable CO₂-to-alcohol electrolysis.