A Molecular Dynamics Simulation Based Investigation of the Proton Conductivity of Anhydrous Pyrazole Doped Poly(Vinylphosphonic Acid) Composite System

With the recognition of the multiple advantages of proton transport membranes that can operate under anhydrous conditions and offer promising opportunities as fuel cells working at high temperatures, a number of such membranes have been developed, but the proton transport mechanism of these materials has not been fully understood. In this work, a theoretical investigation based on molecular dynamics simulations is carried out on a system that is very similar to a real anhydrous proton transport membrane. The location and type of hydrogen bonds have been precisely identified by intermolecular pair correlation functions. Furthermore, analysis of the proton coordination numbers shows that more protons are located in the neighborhood of the oxygen atoms of poly(vinyl phosphonate anion) than in the neighborhood of the nitrogen atoms of pyrazole. The proton conductivity, 1.06 × 10(−3) Scm(−1), is obtained by the self-diffusion coefficient of the protons at 423 K, which is reasonably close to the experimentally measured value, 2 × 10(−4) Scm(−1). In addition, the analysis of the proton trajectories provides us with the proton transfer mechanism in an anhydrous membrane: (a) proton hopping between the oxygen atoms of poly(vinyl phosphonate anion) and (b) proton hopping between two pyrazole molecules. Therefore, the network of the hydrogen bond is the pathway to transport protons via the processes of hydrogen bond forming and breaking.