1H Solid-State NMR Study of Nanothin Nafion Films

The unique behaviors of Nafion nanothin films with thicknesses of 10 nm (ultrathin) and 160 nm (thin) were evaluated using variable-temperature and variable-humidity solid-state 1H NMR spectroscopy. These unprecedented measurements of nanothin films stacked within an NMR rotor represent a remarkable experimental achievement and demonstrate that 1H NMR spectroscopy of such minute amounts of ionomer might be possible within active catalyst layers in polymer electrolyte fuel-cell electrodes. This study was motivated by the observation, in a separate work, of thickness-dependent and highly suppressed conductivity in nanothin films of Nafion (4–300 nm) compared to counterpart free-standing Nafion membranes. Trends in the line width and, more precisely, the T2 relaxation, as probed using a Hahn echo, showed that the local mobility within the hydrogen-bonded domain is equivalent for 10 and 160 nm films and is governed by the fast exchange limit in terms of NMR time scales. Subtle differences in the chemical shif...