▎ 摘　　要

We perform detailed quantum chemical calculations to elucidate the origin and mechanism of the selective permeability of alkali and alkaline earth cation-decorated graphene oxide (M-GO) membranes to organic solvents. The results show that the selectivity is associated mainly with the transport properties of solvents in the membranes, which depends on two regions of the flow path: the sp(3) C-O matrix of the GO sheets and the cation at the center of the hexagon rather than the sp(2) region. According to the delocalization of pi states in sp(2) regions, we propose a design guide for high-quality M-GO membranes. The solvent-cation interaction essentially causes directional transport of molecules in the M-GO membranes under the transmembrane pressure, indicating a site-to-site mechanism. The solvent-sp(3) C-O matrix interaction may inhibit molecular transport between two fixed cations by consuming energy. The competition between energy consumption by the solvent-cation interaction and energy expenditure by the solvent-sp(3) C-O matrix interaction leads to various transport properties of solvents and thus allows for the selective permeability of the M-GO membranes. Findings from the study are helpful for the future design of multifunctional M-GO macro-membranes as cost-effective solution nanofilters in chemical, biological, and medical applications.