Ion Concentration-Dependent Surface Charge Density Inside a Nanopore.

Surface charges shape the electrical double layer (EDL) structure at solid-liquid interfaces, critically influencing the performance of energy storage and micro/nanofluidic devices. However, accurately measuring surface charge density in nanoconfined spaces continues to be a challenge. Here, we introduce a methodology via solid-state nanopores that can investigate the dependence of surface charge density on salt concentrations and nanopore diameters. Measurements, complemented by a theoretical model, reveal that the surface charge density decreases as both the salt concentration in bulk solutions and the nanopore sizes are reduced. Notably, when the salt concentration in the bulk solution drops below 10 -3 M, protons dominate ion conductance in a nanopore, resulting in a constant surface charge density. This study introduces an effective approach to surface charge characterization and may serve in the design of electrokinetically driven nanofluidic systems.