Differentiating Grotthuss Proton Conduction Mechanisms by Nuclear Magnetic Resonance Spectroscopic Analysis of Frozen Samples

Available methods to analyze proton conduction mechanisms cannot distinguish between two proton-conduction processes derived from the Grotthuss mechanism. The two mechanistic variations involve structural diffusion, for which water movement is indispensable, and the recently proposed “packed-acid mechanism,” which involves the conduction of protons without the movement of water and is typically observed in materials consisting of highly concentrated (packed) acids. The latter mechanism could improve proton conductivity under low humidity conditions, which is desirable for polymer electrolyte fuel cells. We proposed a method with which to confirm quantitatively the packed-acid mechanism by combining ²H and ¹⁷O solid-state magic-angle-spinning nuclear magnetic resonance (MAS-NMR) measurement and ¹H pulsed-field gradient (PFG)-NMR analysis. In particular, the measurements were performed below the water-freezing temperature to prevent water movement, as confirmed by the ¹⁷O-MAS-NMR spectra. Even without water movement, the high mobility of protons through short- and long-range proton conduction was observed by using ²H-MAS-NMR and ¹H-PFG-NMR techniques, respectively, in the composite of zirconium sulfophenylphosphonate and sulfonated poly­(arylene ether sulfone) (ZrSPP–SPES), which is a material composed of highly concentrated acids. Such behavior contrasts with that of a material conducting protons through structural diffusion or vehicle mechanisms (SPES), in which the peaks in both ²H and ¹⁷O NMR spectra diminished below water-freezing temperature. The activation energies of short-range proton movement are calculated to be 2.1 and 5.1 kJ/mol for ZrSPP–SPES and SPES, respectively, which indicate that proton conduction in ZrSPP–SPES is facilitated by the packed-acid mechanism. Furthermore, on the basis of the mean-square displacement using the diffusivity coefficient below water-freezing temperature, it was demonstrated that long-range proton movement, of the order of 1.3 μm, can take place in the packed-acid mechanism in ZrSPP–SPES.