Reduced Ionic Conductivity but Enhanced Local Ionic Conductivity in Nanochannels

K Zhou and SP Jiao and Y Chen and HS Qin and YL Liu, LANGMUIR, 37, 12577-12585 (2021).

DOI: 10.1021/acs.langmuir.1c01876

The ionic transport in nanoscale channels with the critical size comparable to ions and solvents shows excellent performance on electrochemical desalination, ion separation, and supercapacitors. However, the key quantity ionic conductivity (sigma) in the nanochannel that evaluates how easily the electric current is driven by an external voltage is still unknown because of the challenges in experimental measurement. In this work, we present an atomistic simulation-based study, which shows that how the ion concentration, nanoconfinement, and heterogeneous solvation modify the ionic conductivity in a two- dimensional graphene nanochannel. We find that sigma in the confined channel is lower than that in the bulk (sigma(b)) at the same concentration along with enhanced ion-ion correlation. However, surprisingly, the local sigma near the channel wall is more conductive than sigma(b) and is about 2-3 folds of the inner layer due to the highly concentrated charge carriers. Based on the layered feature of sigma along the width of the channel, we propose a model that contains two dead (or depletion) layers, two highly conductive layers, and one inner layer to describe the ionic dynamics in the nanochannels. Our findings may open the way to unique nanofluidic functionalities, such as energy harvesting/storage and controlling transport at single-molecule and ion levels using the liquid layer near the wall.

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