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Perm-selective ion transportation in a nanoscale structure has been extensively studied with aids of nanofabrication technology for a decade. While theoretical and experimental advances pushed the phenomenon to seminal innovative applications, its basic observation has relied only on an indirect analysis such as current-voltage relation or fluorescent imaging adjacent to the nanostructures. Here we experimentally, for the first time, demonstrated a direct visualization of perm-selective ion transportation through the nanostructures using an ionic plasma generation. A micro/nanofluidic device was employed for a micro bubble formation, plasma negation and penetration of the plasma through the nanojunction. The direct observation provided a keen evidence of perm-selectivity, i.e. allowing cationic species and rejecting anionic species. Furthermore, we can capture the plasma of Li+, which has lower mobility than Na+ in aqueous state, passed the nanojunction faster than Na+ due to the absence of hydrated shells around Li+. This simple, but essential visualization technique would be effective means not only for advancing the fundamental nanoscale electrokinetic study but also for providing the insight of new innovative engineering applications.

Dielectric microstructures have been reported to have negative influences on perm-selective ion transportation because ions do not migrate in areas where the structures are located. However, the structure can promote the transportation if the membrane is confined to a microscopical scale. In such scale where the area to volume ratio is significantly large, the primary driving mechanisms of the ion transportation are transited from electro-convective instability (EOI) to surface conduction (SC) and electroosmotic flow (EOF). Here we provide rigorous evidence on how SC and EOF around the dielectric microstructures can accelerate the ion transportation by multi-physics simulations and experimental visualizations. The microstructures further polarize the ion distribution by SC and EOF so that ion carriers can travel to the membrane more efficiently. Furthermore, we verified, for the first time, that the arrangements of microstructures have a critical impact on the ion transportation. While convective flows are isolated in crystal pillar configuration, the flows show elongated pattern and create an additional path for ion current in the aligned pillar configuration. Therefore, the fundamental findings of the electrokinetic effects on the dielectric microstructures suggest an innovative application in an energy-efficient micro/nanofluidic devices.

Ion transport in perm-selective media has been extensively investigated in recent years owing to its applications in advancements of fundamental understanding of nanoscale electrokinetics as well as innovative engineering applications. A key phenomenon in this context is ion concentration polarization (ICP) that occurs near perm-selective nanoporous membranes or nanochannels under dc bias. In classical settings, involving voltage-driven transport of ions through perm-selective membranes, concentration polarization is well understood as formation of steep concentration drop to reach near zero concentration (depletion layer) at the anodic side of cation-selective membranes. In contrast to this classical description, we demonstrate here that when ICP is driven in a microchannel and coupled with electroosmotic flows a long-tailed fluorescent layer in front of diffusion layer is formed, which can be characterized as an additional plateau in the concentration profile. Using a micro/nanofluidic platform, in situ visualizations, and local concentration measurements by microelectrode arrays we quantify that this plateau layer has a concentration of 60 % of bulk electrolyte concentration, regardless of the bulk concentration itself. Using a mathematical analysis of conservation laws for flow, charge, and salt, we demonstrate that this plateau region is related to the formation of a flow stagnation point due to the competition between electro-osmotic and induced pressure driven flows. Consistent with the experiments, this analysis predicts the plateau concentration to be 60% of the bulk electrolyte. Thus, this plateau concentration region completes the picture of ICP in microchannels which has drawn significant attention from the fields of electrokinetics and micro/nanofluidics.

Overlimiting current (OLC) through electrolytes interfaced with perm-selective membranes has been extensively researched in recent years for understanding the fundamental mechanisms of transport and developing efficient applications from electrochemistry to sample analysis and separation. Predominant mechanisms responsible for OLC include surface conduction, convection by electro-osmotic flow, and electro-osmotic instability depending on input parameters such as surface charge and geometric constrictions. This work studies how a network of microchannels in a non-uniform array, which mimicks a natural pore configuration, can contribute to OLC. To this end, micro/nanofluidic devices are fabricated with arrays of parallel microchannels with non-uniform size distributions. All cases maintain the same surface and bulk conduction to allow probing the sensitivity only by the non-uniformity of the channels. Both experimental and theoretical current-voltage relations demonstrate that OLCs increase with increasing non-uniformity. Furthermore, the visualization of internal recirculating flows indicates that the non-uniform arrays induce flow loops across the network enhancing advective transport. These evidences confirm a new driving mechanism of OLC, inspired by natural micro/nanoporous materials with random geometric structure. Therefore, this result can advance not only the fundamental understanding of nanoelectrokinetics but also the design rule of engineering applications of electrochemical membrane.