Regulating Interfacial Hydrogen-Bonding Networks by Implanting Cu Sites with Perfluorooctane to Accelerate CO Electroreduction to Ethanol.

Efficient CO electroreduction (CORR) to ethanol holds promise to generate value-added chemicals and harness renewable energy simultaneously. Yet, it remains an ongoing challenge due to the competition with thermodynamically more preferred ethylene production. Herein, we presented a CO reduction predilection switch from ethylene to ethanol (ethanol-to-ethylene ratio of ~5.4) by inherently implanting Cu sites with perfluorooctane to create interfacial noncovalent interactions. The 1.83 %F-CuO organic-inorganic hybrids (OIHs) exhibited an extraordinary ethanol faradaic efficiency (FE) of ∼55.2 %, with an impressive ethanol partial current density of 166 mA cm and excellent robustness over 60 hours of continuous operation. This exceptional performance ranks our 1.83 %F-CuO OIHs among the best-performing ethanol-oriented CORR electrocatalysts. Our findings identified that CF could strengthen the interfacial hydrogen bonding connectivity, which consequently promotes the generation of active hydrogen species and preferentially favors the hydrogenation of *CHCOH to *CHCHOH, thus switching the reaction from ethylene-preferred to ethanol-oriented. The presented investigations highlight opportunities for using noncovalent interactions to tune the selectivity of CO electroreduction to ethanol, bringing it closer to practical implementation requirements.