Non-monotonic variation in the streaming potential in polyelectrolyte grafted nanochannels mediated by ion partitioning effects.

ABSTRACT

BACKGROUND: Polyelectrolyte grafted 'soft' nanochannels are known to enhance electrokinetic energy conversion efficiency, paving the way for a sustainable energy harvesting mechanism. However, the true potential of their efficacy remains to be tapped, as attributed to a deficit in accounting for the interplay between solution pH and ion partitioning effect arising due to permittivity contrast between the coated layer and the bulk media, leading to predictions of an erroneous ionic distribution and a wrongly estimated electrokinetic response. RESULTS: We unravel the electrokinetic behavior of a pH-regulated zwitterionic polyelectrolyte layer grafted nanofluidic system. To this end, we derive a detailed theoretical formulation that considers the nuanced interplay between solution pH and the ion partitioning effect through a thermodynamically consistent ionic distribution. Here, for the first time, we demonstrate a non-monotonic trend in the streaming potential with an increase in the ion partitioning effect, in contrast to a monotonic increase as reported previously. Additionally, we identify a critical permittivity ratio specific to the solution pH at which maximum streaming potential can be obtained. SIGNIFICANCE: We shed light on the counterintuitive effect borne from the increased ion partitioning effect, unveiling a hitherto hidden facet of electrokinetics. By elucidating the delicate balance between solution pH, ion partitioning effect, and polyelectrolyte charge, our findings offer a comprehensive understanding of the multifaceted interplay shaping soft-electrokinetic systems, thereby paving the way for transformative advancements in energy conversion technologies.