Nanopores exhibit a set of interesting
transport properties that
stem from interactions of the passing ions and molecules with the
pore walls. Nanopores are used, for example, as ionic diodes and transistors,
biosensors, and osmotic power generators. Using nanopores is however
disadvantaged by their high resistance, small switching currents in
nA range, low power generated, and signals that can be difficult to
distinguish from the background. Here, we present a mesopore with
ionic conductance reaching μS that rectifies ion current in
salt concentrations as high as 1 M. The mesopore is conically shaped,
and its region close to the narrow opening is filled with high molecular
weight poly-l-lysine. To elucidate the underlying mechanism
of ion current rectification (ICR), a continuum model based on a set
of Poisson–Nernst–Planck and Stokes–Brinkman
equations was adopted. The results revealed that embedding the polyelectrolyte
in a conical pore leads to rectification of the effect of concentration
polarization (CP) that is induced by the polyelectrolyte, and observed
as voltage polarity-dependent modulations of ionic concentrations
in the pore, and consequently ICR. Our work reveals the link between
ICR and CP, significantly extending the knowledge of how charged polyelectrolytes
modulate ion transport on nano- and mesoscales. The osmotic power
application is also demonstrated with the developed polyelectrolyte-filled
mesopores, which enable a power of up to ∼120 pW from one pore,
which is much higher than the reported values using single nanoscale
pores.