Stabilizing Ion Channels via Nonpolar Cross‐Linking in Ion‐Conductive Polymers for Robust CO ₂ ‐to‐Alcohol Conversion

ABSTRACT Efficient alcohol electrosynthesis from CO 2 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 CO 2 ‐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 CO 2 ‐to‐alcohol electrolysis.