Hydroxide Diffusion in Functionalized Cylindrical Nanopores as Idealized Models of Anion Exchange Membrane Environments: An Ab Initio Molecular Dynamics Study

[Image: see text] Anion exchange membranes (AEMs) have attracted significant interest for their applications in fuel cells and other electrochemical devices in recent years. Understanding water distributions and hydroxide transport mechanisms within AEMs is critical to improving their performance as concerns hydroxide conductivity. Recently, nanoconfined environments have been used to mimic AEM environments. Following this approach, we construct nanoconfined cylindrical pore structures using graphane nanotubes (GNs) functionalized with trimethylammonium cations as models of local AEM morphology. These structures were then used to investigate hydroxide transport using ab initio molecular dynamics (AIMD). The simulations showed that hydroxide transport is suppressed in these confined environments relative to the bulk solution although the mechanism is dominated by structural diffusion. One factor causing the suppressed hydroxide transport is the reduced proton transfer (PT) rates due to changes in hydroxide and water solvation patterns under confinement compared to bulk solution as well as strong interactions between hydroxide ions and the tethered cation groups.