Dynamics of hydrated iron(II) cations in nafion polymer membranes

Mössbauer studies of Fe²⁺ in water-soaked nafion polymer membranes in the temperature range between 90 K and 250 K have been performed. Above a critical temperature (～ 180 K) the spectra exhibit both elastic narrow absorption lines and quasielastic broad lines. These spectra are typical of bounded diffusion phenomena observed by Mössbauer spectroscopy in macromolecular systems like haemoglobin, myoglobin and ferritin. Similar spectral shapes have been observed by quasielastic neutron scattering from water in nafion membranes. Within 50 K above the critical temperature the total Mössbauer absorption area decreases by an order of magnitude whereas the narrow absorption line decreases by two orders of magnitude. The results are interpreted in terms of bounded diffusive motion of the iron. Using a model based on overdamped harmonically bound Brownian motion, the essential parameters of the iron motion can be derived as a function of temperature. The iron motion most probably reflects the motion of a large Fe²⁺ complex, e.g. Fe(H₂O)²⁺₆, which is attached to the polymer side chains via the sulphonic group.