Anomalous Solute Diffusivity in Ionic Liquids: Label-Free Visualization and Physical Origins

Dynamic diffusion of molecular solutes in concentrated electrolytes plays a critical role in many applications but is notoriously challenging to measure and model. This challenge is particularly true in the extreme case of ionic liquids (ILs), fluids composed entirely of cations and anions. Solute diffusivities in ILs show a strong concentration dependence, broadening the already vast IL design space and rendering conventional, sample-by-sample measurements impractical for screening. To gain better mechanistic insight into transport in this class of fluids, here we demonstrate a method to visualize the spatiotemporal evolution of concentration fields using microfluidic Fabry-Perot interferometry, enabling diffusivity measurements over an entire composition range within a single experiment. We focus on the absorption and diffusion of water, as both a model solute and a ubiquitous contaminant, within alkylmethylimidazolium-halide ILs. Notably, the Stokes-Einstein relation underpredicts water diffusivities ten- to 50-fold, indicating that water does not experience these ILs as continuum liquids. Based on these measurements, together with wide-angle x-ray scattering and pulsed-field gradient NMR measurements, we propose a new mechanistic framework in which water molecules hop between ion pairs within the IL, which acts as an immobile matrix over timescales relevant for water diffusion. In this case, diffusion is an activated process, with hops between hydrogen-bonding sites over an energetic barrier that decreases linearly with the water fraction. The functional form of the activation energy is consistent with NMR chemical shift measurements, which indicate that hydrogen bonding weakens in linear proportion to the water fraction. This simple model contains the key ingredients required to accurately predict the measured trends in diffusivity-an (Arrhenius) temperature dependence and an exponential composition dependence-for a range of cations, anions, water contents, and temperatures. Our results suggest a general mechanism for anomalously fast diffusion in ILs, where solutes "hop" between binding sites more quickly than the ions rearrange.