Reverse-Selective Anion Separation Relies on Charged "Hourglass" Gate.

According to the hydration size and charge property of separated ions, the transport channel can be constructed to achieve precision ion separation, but the ion geometry as a separation parameter to design the channel structure is rarely reported. Herein, a reverse-selective anion separation membrane composed of a metal-organic frameworks (MOFs) layer with a charged "hourglass" channel as an ion-selective switch to manipulate oxoanion transport is developed. The gate in "hourglass" with tetrahedral geometry similar to the oxoanion (such as SO2- 4, Cr 2O2- 7, and MnO- 4) boosts the transmission effect oxoanion much larger than Cl through geometric matching and Coulomb interaction. Specific channel structure exhibits an abnormal selectivity for SO2- 4/Cl of 20, Cr 2O2- 7/Cl of 6.6, and MnO- 4/Cl of 4.0 in a binary-ion system. The transfer behavior of SO2- 4 in the channel revealed by molecular dynamics simulation and density functional theory calculation further indicates the mechanism of the abnormal separation performance. The universality of the membrane structure is validated by the formation of different nitrogen-containing modified layers, which also achieves in situ growth of the MOFs layer, and exhibits similar reversal separation performance. The geometric configuration control of ion transport channels presents a novel effective strategy to realize the precise separation of target ions.