Overscreening, Co-Ion-Dominated Electroosmosis, and Electric Field Strength Mediated Flow Reversal in Polyelectrolyte Brush Functionalized Nanochannels

TH Pial and HS Sachar and PR Desai and S Das, ACS NANO, 15, 6507-6516 (2021).

DOI: 10.1021/acsnano.0c09248

Controlling the direction and strength of nano-fluidic electrohydrodyanmic transport in the presence of an externally applied electric field is extremely important in a number of nanotechnological applications. Here, we employ all-atom molecular dynamics simulations to discover the possibility of changing the direction of electroosmotic (EOS) liquid flows by merely changing the electric field strength in a nanochannel functionalized with polyelectrolyte (PE) brushes. In exploring this, we have uncovered three facets of nanoconfined PE brush behavior and resulting EOS transport. First, we identify the onset of an overscreening effect: such overscreening refers to the presence of more counterions (Na+) within the brush layer than needed to neutralize the negative brush charges. Accordingly, as a consequence of the overscreening, in the bulk liquid outside the brush layer, there is a greater number of co-ions (Cl-) than counterions in the presence of an added salt (NaCl). Second, this specific ion distribution ensures that the overall EOS flow is along the direction of motion of the co-ions. Such co-ion-dictated EOS transport directly contradicts the notion that EOS flow is always dictated by the motion of the counterions. Finally, for large-enough electric fields, the brush height reduces significantly, causing some of the excess overscreening-inducing counterions to squeeze out of the PE brush layer into the brush-free bulk. As a result, the overscreening effect disappears and the number of co-ions and counterions outside the PE brush layer become similar. Despite that there is an EOS transport, this EOS transport, unlike the standard EOS transport that occurs due to the imbalance of the co-ions and counterions, occurs since a larger residence time of the water molecules in the first solvation shell of the counterions (Na+) ensures a water transport in the direction of motion of the counterions. The net effect is the reversal of the direction of the EOS transport by merely changing the strength of the electric field.

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