A molecular theory for predicting the thermodynamic efficiency of electrokinetic energy conversion in slit nanochannels.

The classical density functional theory is incorporated with the Stokes equation to examine the thermodynamic efficiency of pressure-driven electrokinetic energy conversion in slit nanochannels. Different from previous mean-field predictions, but in good agreement with recent experiments, the molecular theory indicates that the thermodynamic efficiency may not be linearly correlated with the channel size or the electrolyte concentration. For a given electrolyte, an optimal slit nanochannel size and ion concentration can be identified to maximize both the electrical current and the thermodynamic efficiency. The optimal conditions are sensitive to a large number of parameters including ion diameters, valences, electrolyte concentration, channel size, and the valence- and size-asymmetry of oppositely charged ionic species. The theoretical results offer fresh insights into pressure-driven current generation processes and are helpful guidelines for the design of apparatus for the electrokinetic energy conversion.