Hydrophobic assembly of molecular catalysts at the gas-liquid-solid interface drives highly selective CO₂...

Molecular catalysts offer tunable active and peripheral sites, rendering them ideal model systems to explore fundamental concepts in catalysis. However, hydrophobic designs are often regarded as detrimental for dissolution in aqueous electrolytes. Here we show that established cobalt terpyridine catalysts modified with hydrophobic perfluorinated alkyl side chains can assemble at the gas-liquid-solid interfaces on a gas diffusion electrode. We find that the self-assembly of these perfluorinated units on the electrode surface results in a catalytic system selective for electrochemical CO₂ reduction to CH₄, whereas every other cobalt terpyridine catalyst reported previously was only selective for CO or formate. Mechanistic investigations suggest that the pyridine units function as proton shuttles that deliver protons to the dynamic hydrophobic pocket in which CO₂ reduction takes place. Finally, integration with fluorinated carbon nanotubes as a hydrophobic conductive scaffold leads to a Faradaic efficiency for CH₄ production above 80% at rates above 10 mA cm^-2-impressive activities for a molecular electrocatalytic system.