Anionic Ionomer: Released Surface-Immobilized Cations and an Established Hydrophobic Microenvironment for Efficient and Durable CO₂-to-Ethylene Electrosynthesis at High Current over One Month

Electrosynthesis of multicarbon products, such as C₂H₄, from CO₂ reduction on copper (Cu) catalysts holds promise for achieving carbon neutrality. However, maintaining a steady high current-level C₂H₄ electrosynthesis still encounters challenges, arising from unstable alkalinity and carbonate precipitation caused by undesired ion migration at the cathode under a repulsive electric field. To address these issues, we propose a universal “charge release” concept by incorporating tiny amounts of an oppositely charged anionic ionomer (e.g., perfluorinated sulfonic acid, PFSA) into a cationic covalent organic framework on the Cu surface (cCOF/PFSA). This strategy effectively releases the hidden positive charge within the cCOF, enhancing surface immobilization of cations to impede both outward migration of generated OH^- and inward migration of cations, inhibiting carbonate precipitation and creating a strong alkaline microenvironment. Meanwhile, the ionomer’s hydrophobic chains create a hydrophobic environment within the cCOF, facilitating efficient gas transport. In situ characterizations and theoretical calculations demonstrate that the cCOF/PFSA catalyst establishes a hydrophobic strong alkaline microenvironment, optimizing the adsorption strength and configuration of *CO intermediates to promote the C₂H₄ formation. The optimized catalyst achieves a 70.5% Faradaic efficiency for C₂H₄ with a partial current density over 470 mA cm^-2. Notably, it delivers a high single-pass carbon efficiency of 96.5% for CO₂RR and sustains an exceptional stability over 760 h. When implemented in a large-area MEA electrolyzer and a 5-cell MEA stack, the system achieves an industrial current of 15 A and continuous C₂H₄ production exceeding 19 mL min^-1, marking a significant step toward industrial feasibility in CO₂RR-to-C₂H₄ conversion.