Overlimiting current (OLC) is a non-linear current response that occurs related to an ion concentration polarization (ICP) phenomenon in micro/nanofluidic systems and holds great importance since it represents the rate of selective ion transportation through perm-selective structure. For last two decades, numerous studies of OLC have been reported about understanding the fundamentals of nanoelectrokinetics and enhancing ion transportation through perm-selective membranes. Recent study reported that the alignment of non-uniform microspace near the perm-selective membranes in two-dimensional micro/nanofluidic systems can significantly enhance OLC, i.e., overlimiting conductance (σOLC). This is attributed to recirculation flow induced by combination of unbalanced electroosmosis and induced pressure driven flow among non-uniform microspaces. However, 2D micro/nanofluidic systems have limited practicality due to their small volume and low throughput. Herein, we tested the OLC enhancement using 3D-printed hierarchical micro/nanofluidic systems with respect to the non-uniformity of microspaces. The 3D microspaces were fabricated as a mesh structure using a conventional 3D printer. By comparing current–voltage measurement with each type of mesh, we experimentally confirmed the generation of recirculation flow among non-uniform meshes and ionic current enhancement in 3D hierarchical micro/nanofluidic system. Also, we further investigated the enhancement of overlimiting conductance depending on the mesh pattern. Furthermore, we validated that this effect of microscale non-uniform compartmentalization, both increasing surface area and aligning non-uniform spaces, appears not only at low molar concentration but at high molar concentrations. This demonstration can offer a strategy to design optimal electrochemical systems where a perm-selective ion transportation is crucial.
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