Direct evidence is provided for the transition from surface conduction (SC) to electro-osmotic flow (EOF) above a critical channel depth (d) of a nanofluidic device. The dependence of the overlimiting conductance (OLC) on d is consistent with theoretical predictions, scaling as d −1 for SC and d 4=5 for EOF with a minimum around d ¼ 8 μm. The propagation of transient deionization shocks is also visualized, revealing complex patterns of EOF vortices and unstable convection with increasing d. This unified picture of surface-driven OLC can guide further advances in electrokinetic theory, as well as engineering applications of ion concentration polarization in microfluidics and porous media.

In this work, we experimentally investigated an effect of the hydrodynamic convective flow on ion transport through a nanoporous membrane in a micro/nanofluidic modeled system. The convective motion of ions in an ion concentration polarization (ICP) layer was controlled by external hydrodynamic inflows adjacent to the nanoporous membrane. The ion depletion region, which is regarded as a high electrical resistance, was spatially confined to a triangular shape with the additional hydrodynamic convective flow, resulting in a significant alteration in the classical ohmic-limiting-overlimiting current characteristics. Furthermore, the extreme spatial confinement can completely eliminate the limiting current region at a higher flow rate, while the ICP layer still exists. The presented results enable one to obtain a high current value which turns out to be a high electrical power efficiency. Therefore, this mechanism could be utilized as an optimizing power consumption strategy for various electrochemical membrane systems such as fuel-cells, electro-desalination systems and nanofluidic preconcentrators, etc.

Ion concentration polarization (ICP) is a fundamental electrokinetic process that occurs near a perm-selective membrane under dc bias. Overall process highly depends on the current transportation mechanisms such as electro-convection, surface conduction and diffusioosmosis and the fundamental characteristics can be significantly altered by external parameters, once the permselectivity was fixed. In this work, a new ICP device with a bifurcated current path as for the enhancement of the surface conduction was fabricated using a polymeric nanoporous material. It was protruded to the middle of a microchannel, while the material was exactly aligned at the interface between two microchannels in a conventional ICP device. Rigorous experiments revealed out that the propagation of ICP layer was initiated from the different locations of the protruded membrane according to the dominant current path which was determined by a bulk electrolyte concentration. Since the enhancement of surface conduction maintained the stability of ICP process, a strong electrokinetic flow associated with the amplified electric field inside ICP layer was significantly suppressed over the protruded membrane even at condensed limit. As a practical example of utilizing the protruded device, we successfully demonstrated a non-destructive micro/nanofluidic preconcentrator of fragile cellular species (i.e. red blood cells).

To overcome a world-wide water shortage problem, numerous desalination methods have been developed with state-of-the-art power efficiency. Here we propose a spontaneous desalting mechanism referred to as the capillarity ion concentration polarization. An ion-depletion zone is spontaneously formed near a nanoporous material by the permselective ion transportation driven by the capillarity of the material, in contrast to electrokinetic ion concentration polarization which achieves the same ion-depletion zone by an external d.c. bias. This capillarity ion concentration polarization device is shown to be capable of desalting an ambient electrolyte more than 90% without any external electrical power sources. Theoretical analysis for both static and transient conditions are conducted to characterize this phenomenon. These results indicate that the capillarity ion concentration polarization system can offer unique and economical approaches for a power-free water purification system.

The first experimental and theoretical evidence was provided for the non-negligible role of a diffusio-osmosis in the ion concentration polarization (ICP) layer, which had been reported to be in a high Peclet number regime. Under the assumption that the hydrated shells of cations were stripped out with the amplified electric field inside the ICP layer, its concentration profile possessed a steep concentration gradient at the stripped location. Since the concentration gradient drove a strong diffusio-osmosis, the combination of electro-osmotic and diffusio-osmotic slip velocity had a form of an anomalous nonmonotonic function with both a single- and multiple-cationic solution. A direct measurement of electrolytic concentrations around the layer quantitatively validated our new investigations. This non-negligible diffusio-osmotic contribution in a micro- and nanofluidic platform or porous medium would be essential for clarifying the fundamental insight of nanoscale electrokinetics as well as guiding the engineering of ICP-based electrochemical systems.