Tetraalkylammonium Cations Conduction through a Single Nanofluidic Diode: Experimental and Theoretical Studies

[EN] We describe experimentally and theoretically the concentration-dependent conduction of tetraalkylammonium (TAA+) cations through a nanofluidic diode fabricated in a polymer membrane via asymmetric track-etching techniques. This single-pore membrane exhibits current rectification characteristics because of the ionized carboxylate groups on the pore surface. We use aqueous solutions of potassium (K+ ), ammonium (A+ ), tetramethylammonium (TMA+ ), tetraethylammonium (TEA+ ), and tetrabutylammonium (TBA+ ) ions with concentrations ranging from 50 to 500 mM under acidic (pH 3.5) and physiological (pH 6.5) conditions. Compared with the K+ and A+ ions, the TMA+ , TEA+ , and TBA+ ions show relatively low rectified ion currents because the cation hydrophobicity increases with the alkyl chain. At low concentrations and acidic conditions, an inversion in the current rectification characteristics is observed, which is attributed to the adsorption of the organic cations on the pore surfaces. The experimental results can be analyzed in terms of the Poisson-Nernst-Planck equations and the geometrical and electrical single pore characteristics for the different ions, pH values, and salt concentrations employed. This theoretical approach is qualitative and could be extended further to include a self-consistent theoretical treatment of the ionic adsorption and surface charge equilibria