Hydrodynamic slip of alkali chloride solutions in uncharged graphene nanochannels

A Kunhunni and SK Kannam and SP Sathian and BD Todd and PJ Daivis, JOURNAL OF CHEMICAL PHYSICS, 156, 014704 (2022).

DOI: 10.1063/5.0054681

Using non-equilibrium molecular dynamics simulations, we demonstrate the effect of concentration and alkali cation types (K+, Na+, and Li+) on the hydrodynamic slip of aqueous alkali chloride solutions in an uncharged graphene nanochannel. We modeled the graphene-electrolyte interactions using the potential of Williams et al. J. Phys. Chem. Lett. 8, 703 (2017), which uses optimized graphene-ion Lennard-Jones interaction parameters to effectively account for surface and solvent polarizability effects on the adsorption of ions in an aqueous solution to a graphene surface. In our study, the hydrodynamic slip exhibits a decreasing trend for alkali chloride solutions with increasing salt concentration. The NaCl solution shows the highest reduction in the slip length followed by KCl and LiCl solutions, and the reduction in the slip length is very much dependent on the salt type. We also compared the slip length with that calculated using a standard unoptimized interatomic potential obtained from the Lorentz-Berthelot mixing rule for the ion-carbon interactions, which is not adjusted to account for the surface and solvent polarizability at the graphene surface. In contrast to the optimized model, the slip length of alkali chloride solutions in the unoptimized model shows only a nominal change with salt concentration and is also independent of the nature of salts. Our study shows that adoption of the computationally inexpensive optimized potential of Williams et al. for the graphene-ion interactions has a significant influence on the calculation of slip lengths for electrolyte solutions in graphene-based nanofluidic devices.

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