Understanding the K⁺/Na⁺-Selectivity-Enabled Osmotic Power Generation: High Selectivity May Not Be Indispensable

By mixing ionic solutions, considerable energy can be harvested from entropy change. Recently, we proposed a concept of potassium-permselectivity enabled osmotic power generation (PoPee-OPG) by mixing equimolar KCl and NaCl solutions via artificial potassium ion channels (APICs, Natl. Sci. Rev. 2023, 10, nwad260). However, a fundamental understanding of the relationship between the K⁺/Na⁺ selectivity and optimal performance remains unexplored. Herein, we establish a primitive molecular thermodynamic model to investigate the energy extraction process. We find PoPee-OPG differs from previous charge-selectivity-based techniques, such as the salinity gradient power generation, in two distinct ways. First, the extractable energy density and efficiency positively depend on concentration. More surprisingly, a very high potassium selectivity is not indispensable for satisfactory efficiency and energy density. An optimal K⁺/Na⁺ selectivity region of 3 to 10 is found. This somewhat counterintuitive discovery provides a renewed understanding of the emerging PoPee-OPG, and it predicts a broad applicability among existing APICs.