Real-time visualisation of ion exchange in molecularly confined spaces where electric double layers overlap.

ABSTRACT

Ion interactions with interfaces and transport in confined spaces, where electric double layers overlap, are essential in many areas, ranging from crevice corrosion to understanding and creating nano-fluidic devices at the sub 10 nm scale. Tracking the spatial and temporal evolution of ion exchange, as well as local surface potentials, in such extreme confinement situations is both experimentally and theoretically challenging. Here, we track in real-time the transport processes of ionic species (LiClO4) confined between a negatively charged mica surface and an electrochemically modulated gold surface using a high-speed in situ sensing Surface Forces Apparatus. With millisecond temporal and sub-micrometer spatial resolution we capture the force and distance equilibration of ions in the confinement of D ≈ 2-3 nm in an overlapping electric double layer (EDL) during ion exchange. Our data indicate that an equilibrated ion concentration front progresses with a velocity of 100-200 µm s-1 into a confined nano-slit. This is in the same order of magnitude and in agreement with continuum estimates from diffusive mass transport calculations. We also compare the ion structuring using high resolution imaging, molecular dynamics simulations, and calculations based on a continuum model for the EDL. With this data we can predict the amount of ion exchange, as well as the force between the two surfaces due to overlapping EDLs, and critically discuss experimental and theoretical limitations and possibilities.