Electron–electrolyte coupling in AC transport through nanofluidic channels

Abstract

The transport properties of nanofluidic channels are usually studied under constant (DC) voltage or pressure driving. However, the frequency response under sinusoidal (AC) drivings offers rich insights into the time-dependent transport mechanisms. Inspired by recent electrochemical approaches, we investigate the couplings between ionic and electronic transport under AC driving. We show that conduction electrons of the channel walls participate in ionic current via capacitive electrochemical coupling, defining a critical frequency and length scale where electron-dominated conductivity emerges. We further analyze how electron–ion coupling modifies electro-osmotic flows and demonstrate that fluctuation-induced momentum transfer between the electrolyte and wall electrons produces distinct AC transport signatures, depending on the charge carrier polarity. Altogether, we establish a frequency-dependent transport matrix that couples ionic, electronic, and hydrodynamic flows. These findings establish AC nanofluidic transport as a powerful probe of interfacial phenomena under confinement and suggest new directions for engineering nanofluidic functionalities through electron–electrolyte coupling.