ArticleMembranes2026
Understanding Vanadium Ion Diffusion in Nafion Using an Atomistic Study and Microscopic Concentration Profiles.
Article in Membranes, 2026. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Not yet cited in PubMed.
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Abstract
The functionality of ionomeric membranes is influenced by small changes of several parameters. Aqueous network formation by phase separation between the hydrophilic and hydrophobic parts of the polymer is one critical factor for water and ion transport. In particular, the transport of highly charged ions like V3+ is not well understood. The unsteady diffusion in Nafion, a sulfonic acid based cation exchange polymer, using V3+ profiles obtained with micro X-ray fluorescence (0.5 μm spot over a 180 μm scan) yields a diffusion coefficient of 4×10-13 m2s-1 at λH2O/SO3=12 and at ca. 20 °C. It is confirmed that the concentration profile can be described by an error function formalism. The diffusivity, determined from the entire profile, represents mainly the transport into a vanadium free environment with very low ionic strength as the membrane was conditioned in ultra-pure water. The macroscopic ion transport is influenced by local molecular interactions, interconnection of water pockets and long range ionic interactions. The local interactions of V3+ were studied using molecular dynamics (MDs) simulations. The MD simulation studies diffusion at a constant ion concentration and short length scale (ca. 30 nm). It gives insights on the effects of dissolved V3+ ions on the local structure. Radial distribution functions reveal that at low hydration, the vanadium ions have an ordering effect on water molecules. The diffusion coefficient of V3+ is determined on a molecular level from the mean-square displacement yielding 2.5×10-10 m2s-1 for V3+ ions at a membrane water content of λH2O/SO3 = 6. The phenomenon in which the diffusivity decreases over longer length scales was documented before for water and H+ in Nafion; however, this was by only about one order of magnitude. The experimental microscopic approach described by us is universally applicable, e.g., to environments of higher ionic strength, ions with different charges, and different types of ion-exchange membranes. Longer diffusion times allow us to distinguish between different concentration regimes.
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