Abstract
Polyamide membranes, such as nanofiltration (NF) membranes, are widely used for water purification. However, the mechanisms of solute transport and solute rejection due to solute charge interactions with the membrane remain unclear at the molecular level. Here, we use molecular dynamics simulations to examine the transport of single-solute feeds through charged nanofiltration membranes with different membrane charge concentrations of COO- and NH+2 resulting from the deprotonation or protonation of polymeric end groups according to the pH level that the membrane experiences. The results show that Na+ and Cl- solute ions are better rejected when the membrane has a higher concentration of negatively charged groups, corresponding to a higher pH, whereas CaCl2 is well rejected at all pH levels studied. These results are consistent with those of experiments performed at the same pH conditions as the simulation setup. Moreover, solute transport behavior depends on the membrane functional group distribution. When COO- functional groups are concentrated at membrane feed surface, ion permeation into the membrane is reduced. Counter-ions tend to associate with charged functional groups while co-ions seem to pass by the charged groups more easily. In addition, steric effects play a role when ions of opposite charge cluster in pores of the membrane. This study reveals solute transport and rejection mechanisms related to membrane charge and provides insights into how membranes might be designed to achieve specific desired solute rejection.