Ion transport through short nanopores modulated by charged exterior surfaces.

Short nanopores find extensive applications, capitalizing on their high throughput and detection resolution. Ionic behaviors through long nanopores are mainly determined by charged inner-pore walls. When pore lengths decrease to sub-200 nm, charged exterior surfaces provide considerable modulation to ion current. We find that the charge status of inner-pore walls affects the modulation of ion current from charged exterior surfaces. For 50-nm-long nanopores with neutral inner-pore walls, the charged exterior surfaces on the voltage (surfaceV) and ground (surfaceG) sides enhance and inhibit the ion transport by forming ion enrichment and depletion zones inside nanopores, respectively. For nanopores with both charged inner-pore and exterior surfaces, continuous electric double layers enhance the ion transport through nanopores significantly. The charged surfaceV results in higher ion current by simultaneously weakening the ion depletion at pore entrances and enhancing the intra-pore ion enrichment. The charged surfaceG expedites the exit of ions from nanopores, resulting in a decrease in ion enrichment at pore exits. Through adjustment in the width of charged-ring regions near pore boundaries, the effective charged width of the charged exterior is explored at ∼20 nm. Our results may provide a theoretical guide for further optimizing the performance of nanopore-based applications, such as seawater desalination, biosensing, and osmotic energy conversion.