Elucidating the ionomer-electrified metal interface.

The competitive adsorption of Nafion functional groups induce complex potential dependencies (Stark tuning) of vibrational modes of CO adsorbed (CO(ads)) on the Pt of operating fuel cell electrodes. Operando infrared (IR) spectroscopy, polarization modulated IR spectroscopy (PM-IRRAS) of Pt-Nafion interfaces, and attenuated total reflectance IR spectroscopy of bulk Nafion were correlated by density functional theory (DFT) calculated spectra to elucidate Nafion functional group coadsorption responsible for the Stark tuning of CO(ads) on high surface area fuel cell electrodes. The DFT calculations and observed spectra suggest that the side-chain CF3, CF2 groups (i.