Fluorinated polymer zwitterions on gold nanoparticles: patterned catalyst surfaces guide interfacial transport and electrochemical CO 2 reduction.

We report the use of fluorinated polymer zwitterions to build hybrid systems for efficient CO 2 electroreduction. The unique combination of hydrophilic phosphorylcholine and hydrophobic fluorinated moieties in these polymers creates a fractal structure with mixed branched cylinders on the surface of gold nanoparticles (AuNPs). In the presence of these polymers, the CO faradaic efficiency improves by 50-80% in the range of -0.7 V to -0.9 V. The fractal structures have a domain size of ∼3 nm, showing enhanced mass transfer kinetics of CO 2 approaching the catalyst surfaces without limiting ion diffusion. The phase-separated hydrophilic and hydrophobic domains offer separated channeling to water and CO 2 , as confirmed by attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and molecule dynamic (MD) simulations. H 2 O molecules permeate extensively into the polymer layer that adsorbs on zwitterions, forming continuous chains, while CO 2 molecules strongly associate with the fluorinated tails of fluorinated polyzwitterions, with oxygen facing the positively charged amine groups. Overall, this coupling of zwitterion and fluorocarbon in a polymer material creates new opportunities for defining microenvironments of metallic nanocatalysts in hybrid structures.