Simultaneous Energy Generation and Flow Enhancement () in Polyelectrolyte Brush Functionalized Nanochannels.

Energy generation through nanofluidics is a topic of great nanotechnological relevance. Here, we conduct all-atom molecular dynamics (MD) simulations of the transport of water and ions in a pressure-driven flow in nanochannels grafted with charged polyelectrolyte (PE) brushes and discover the possibility of simultaneous electrokinetic energy generation and flow enhancement (henceforth denoted as the ). Such PE-brush-functionalized nanochannels have been recently shown to demonstrate an overscreening (OS) effect (characterized by the presence of a greater number of screening counterions within the PE brush layer than needed to screen the PE brush charges), a consequent presence of excess co-ions within the PE brush-free bulk, and a co-ion-driven electroosmotic (EOS) transport in the presence of small to moderate applied axial electric fields. In this study, however, we find that the streaming current, which represents the current generated by the flow-driven downstream advection of the charge imbalance present within the electric double layer (EDL) that screens the PE brush charges, is governed by the migration of the counterions. This stems from the fact that the highest contribution to the overall streaming current arises from the region near the PE brush-water interface (where there is an excess of counterions), while the brush-free bulk yields a hitherto unreported, but small, co-ion-dictated streaming current. This downstream advection of the charge imbalance (and the resultant counterion-driven streaming current) eventually leads to the development of an electric field (streaming electric field) in the direction that is opposite the direction of the counterion-driven streaming current. The streaming current and the streaming electric field interact to generate the electrokinetic energy. Equally important, this streaming electric field induces an EOS transport, which becomes co-ion-driven, due to the presence of excess co-ions in the brush-free bulk. For the case of nanochannels grafted with negatively charged PE brushes, the streaming electric field will be in a direction that is opposite that of the pressure-driven transport, and hence the co-ion (or anion) driven EOS flow will be in the same direction as the pressure-driven transport. On the other hand, for the case of nanochannels grafted with positively charged PE brushes, the streaming electric field will be in the same direction as the pressure-driven flow, and hence the co-ion (or cation) driven EOS flow, will again be in the same direction as the pressure-driven flow. Therefore, whenever there occurs a presence of the OS and the resulting co-ion-driven EOS transport in PE brush grafted nanochannels, regardless of the sign of the charges of the PE brushes, this EOS transport will always the pressure-driven transport and will cause the most fascinating increase in the net volume flow rate across the nanochannel cross section, which is the .