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The dynamics of water and its effect on proton transport kinetics in Nafion membranes are compared at several hydration levels. Nafion is the most widely used polyelectrolyte membrane in fuel cells. Ultrafast infrared spectroscopy of the O-D stretch of dilute HOD in H2O provides a probe of the local environment and hydrogen bond network dynamics of water confined in the hydrophilic regions of Nafion. The kinetics of proton transfer in Nafion are tracked by following the excited-state proton transfer and recombination kinetics of a molecular probe, pyranine (HPTS). The hydrophilic domains of Nafion grow with increased hydration, and the interfacial regions reorganize, leading to a changing local environment for water near the interface. Swelling is not uniform throughout the membrane, and heterogeneity is observed in the fluorescence anisotropy decays of the methoxy derivative of pyranine. Measurements of the time-dependent anisotropy of water in Nafion provide a direct probe of the hydrogen bond network dynamics. These dynamics, as well as the rate of proton transport over nanoscopic distances, are observed to slow significantly as the hydration level of the membrane decreases. The results provide insights into the influence of changes in the dynamics of water on the proton-transfer processes. |
