Diameter-Dependent Multiple Proton Jumps Dictate Hydronium and Hydroxide Transport in Carbon Nanotubes

Abstract

Nanofluidic channels impose extreme confinement on water, giving rise to unusual transport phenomena of the liquid. However, how transport of hydroxide and hydronium ions is influenced by such confinement is still not fully understood. This study employs machine learning-accelerated simulations, based on SCAN density functional, to investigate proton transfer dynamics in CNTs of varying diameters (0.8 nm to 2.8 nm). The extreme confinement of water inside 0.8 nm CNT not only enhances the probability of multiple consecutive proton jumps, but also reverses the relative diffusion coefficient of hydronium and hydroxide ions in bulk water. In CNTs with diameters larger than 0.8 nm, hydronium diffuses slightly faster than in bulk, whereas hydroxide diffusion slows because of its localization near CNT walls, hindering multiple proton jumps. This work highlights the significant impact of nanoscale confinement on proton transfer dynamics, with implications for designing nanoscale systems with controlled proton transport.