From nanotubes to nanoholes: Scaling of selectivity in uniformly charged nanopores through the Dukhin number for 1:1 electrolytes

Scaling of the behavior of a nanodevice means that the device function (selectivity) is a unique smooth and monotonic function of a scaling parameter that is an appropriate combination of the system's parameters. For the uniformly charged cylindrical nanopore studied here, these parameters are the electrolyte concentration, c, voltage, U, the radius and the length of the nanopore, R and H, and the surface charge density on the nanopore's surface, sigma. Due to the non-linear dependence of selectivities on these parameters, scaling can only be applied in certain limits. We show that the Dukhin number, Du=|sigma|/eRc similar to|sigma|lambda D2/eR (lambda (D) is the Debye length), is an appropriate scaling parameter in the nanotube limit (H -> infinity). Decreasing the length of the nanopore, namely, approaching the nanohole limit (H -> 0), an alternative scaling parameter has been obtained, which contains the pore length and is called the modified Dukhin number: mDu similar to Du H/lambda (D) similar to |sigma|lambda H-D/eR. We found that the reason for non-linearity is that the double layers accumulating at the pore wall in the radial dimension correlate with the double layers accumulating at the entrances of the pore near the membrane on the two sides. Our modeling study using the Local Equilibrium Monte Carlo method and the Poisson-Nernst-Planck theory provides concentration, flux, and selectivity profiles that show whether the surface or the volume conduction dominates in a given region of the nanopore for a given combination of the variables. We propose that the inflection point of the scaling curve may be used to characterize the transition point between the surface and volume conductions.

Automated summary

Scaling of the behavior of a nanodevice involves a unique and smooth function of a scaling parameter, with the Dukhin number serving as an appropriate parameter for certain limits. The non-linear dependence of selectivities on system parameters necessitates the use of alternative scaling parameters in different limits of nanopore length.