TY - JOUR

T1 - Exploring the pore charge dependence of K+ and Cl- permeation across a graphene monolayer

T2 - a Molecular Dynamics study

AU - Guardiani, Carlo

AU - Gibby, William A T

AU - Barabash, Miraslau L

AU - Luchinsky, Dmitry G

AU - McClintock, Peter V E

PY - 2019/7/1

Y1 - 2019/7/1

N2 - Selective permeation through graphene nanopores is attracting increasing interest as an efficient and cost-effective technique for water desalination and purification. In this work, using umbrella sampling and molecular dynamics simulations with constant electric field, we analyze the influence of pore charge on potassium and chloride ion permeation. As pore charge is increased, the barrier of the potential of mean force (PMF) gradually decreases until it turns into a well split in two subminima. While in the case of K+ this pattern can be explained as an increasing electrostatic compensation of the desolvation cost, in the case of Cl􀀀 the pattern can be attributed to the accumulation of a concentration polarization layer of potassium ions screening pore charge. Th analysis of potassium PMFs in terms of forces revealed a conflicting influence on permeation of van der Waals and electrostatic forces that both undergo an inversion of their direction as pore charge is increased. Even if the most important transition involves the interplay between the electrostatic forces exerted by graphene and water, the simulations also revealed an important role of the changing distribution of potassium and chloride ions. The influence of pore charge on the orientation of water molecules was also found to affect the van der Waals forces they exert on potassium.

AB - Selective permeation through graphene nanopores is attracting increasing interest as an efficient and cost-effective technique for water desalination and purification. In this work, using umbrella sampling and molecular dynamics simulations with constant electric field, we analyze the influence of pore charge on potassium and chloride ion permeation. As pore charge is increased, the barrier of the potential of mean force (PMF) gradually decreases until it turns into a well split in two subminima. While in the case of K+ this pattern can be explained as an increasing electrostatic compensation of the desolvation cost, in the case of Cl􀀀 the pattern can be attributed to the accumulation of a concentration polarization layer of potassium ions screening pore charge. Th analysis of potassium PMFs in terms of forces revealed a conflicting influence on permeation of van der Waals and electrostatic forces that both undergo an inversion of their direction as pore charge is increased. Even if the most important transition involves the interplay between the electrostatic forces exerted by graphene and water, the simulations also revealed an important role of the changing distribution of potassium and chloride ions. The influence of pore charge on the orientation of water molecules was also found to affect the van der Waals forces they exert on potassium.

U2 - 10.1039/C9RA03025E

DO - 10.1039/C9RA03025E

M3 - Journal article

VL - 9

SP - 20402

EP - 20414

JO - RSC Advances

JF - RSC Advances

SN - 2046-2069

IS - 35

ER -