Modulation of Ionic Current Rectification in Short Bipolar Nanopores.

Bipolar nanopores, with asymmetric charge distributions, can induce significant ionic current rectification (ICR) at ultrashort lengths, finding potential applications in nanofluidic devices, energy conversion, and other related fields. Here, with simulations, we investigated the characteristics of ion transport and modulation of the ICR inside bipolar nanopores. With bipolar nanopores of half-positive and half-negative surfaces, the most significant ICR phenomenon appears at various concentrations. In these cases, the ICR ratios are independent of electrolyte types. In other cases where nanopores have oppositely charged surfaces of different lengths, ICR ratios are related to the mobility of anions and cations. The pore length and surface charge density can enhance ICR. As the pore length increases, ICR ratios first increase and then approach their saturation, which is determined by the surface charge density. External surface charges of nanopores can promote the ICR phenomenon mainly due to the enhancement of ion enrichment inside the nanopores by external surface conductance. The effective width of exterior charged surfaces under various conditions is also explored, which is inversely proportional to the pore length and salt concentration and linearly related to the pore diameter, surface charge density, and applied voltage. Our results may provide guidance for the design of bipolar porous membranes.