Surface modification of polyamide reverse osmosis membranes with small-molecule zwitterions for enhanced fouling resistance: a molecular simulation study

Surface modification with small-molecule zwitterions is experimentally proved to be an effective solution to improve the antifouling performance of polyamide membranes. However, there is no comprehensive understanding of their microscopic mechanism. In order to address this issue, in this work we constructed two atomistic models, PA (a pure polyamide membrane) and QDAP-PA (a polyamide membrane surface-modified with QDAP), where QDAP was a zwitterion that was prepared by 2,6-daaminopyridine quaternized with 3-bromopropionic acid experimentally. Density functional theory was adopted to elucidate the variations in the electrostatic potential before and after modification. Then, equilibrium molecular dynamics (EMD) simulations were conducted to investigate the structure and hydrophobic/hydrophilic nature of the membrane surface in the two models. Finally, we introduced two typical organic foulants, sodium dodecyl sulfonate (SDS) and dodecyl trimethyl ammonium chloride (DTAC), to evaluate the antifouling performance of the membranes with the umbrella sampling method. The analyses of the membrane structure and properties show that surface modification with small-molecule zwitterions can densify the membrane surface as well as enlarge the distribution of electrostatic potential on the membrane surface. Water molecules tend to have more interactions with the membrane and more hydrogen bonds near the membrane surface are observed in QDAP-PA. The antifouling test supports that QDAP-PA shows a better antifouling performance, as the surface-modified membrane exhibits a stronger resistance to SDS and DTAC. Even if the foulant is adsorbed to the membrane surface, the denser interface region can prevent a further pollution of the foulant. Also, the free energy needed during the process for QDAP-PA to desorb a foulant is relatively small, indicating that this kind of membrane is easy to clean. The current work might provide a comprehensive understanding of the enhanced fouling resistance of polyamide membranes after surface modification with small-molecule zwitterions.