Perfluoroalkyl Phosphonic and Phosphinic Acids as Proton Conductors for Anhydrous Proton-Exchange Membranes

A study of proton‐transport rates and mechanisms under anhydrous conditions using a series of acid model compounds, analogous to comb‐branch perfluorinated ionomers functionalized with phosphonic, phosphinic, sulfonic, and carboxylic acid protogenic groups, is reported. Model compounds are characterized with respect to proton conductivity, viscosity, proton, and anion (conjugate base) self‐diffusion coefficients, and Hammett acidity. The highest conductivities, and also the highest viscosities, are observed for the phosphonic and phosphinic acid model compounds. Arrhenius analysis of conductivity and viscosity for these two acids reveals much lower activation energies for ion transport than for viscous flow. Additionally, the proton self‐diffusion coefficients are much higher than the conjugate‐base self‐diffusion coefficients for these two acids. Taken together, these data suggest that anhydrous proton transport in the phosphonic and phosphinic acid model compounds occurs primarily by a structure‐diffusion, hopping‐based mechanism rather than a vehicle mechanism. Further analysis of ionic conductivity and ion self‐diffusion rates by using the Nernst–Einstein equation reveals that the phosphonic and phosphinic acid model compounds are relatively highly dissociated even under anhydrous conditions. In contrast, sulfonic and carboxylic acid‐based systems exhibit relatively low degrees of dissociation under anhydrous conditions. These findings suggest that fluoroalkyl phosphonic and phosphinic acids are good candidates for further development as anhydrous, high‐temperature proton conductors. Proton‐transport mechanisms: A conclusive explanation for the basic proton‐transport mechanisms under anhydrous conditions in perfluorinated phosphonic, phosphinic, sulfonic, and carboxylic acid systems is offered (see figure). Proton hopping or structure diffusion is proposed for the perfluorinated phosphonic and phosphonic acids, whereas a vehicle mechanism is proposed for the perfluorinated sulfonic acid and carboxylic acids systems.