Covalent–Organic‐Framework Membrane with Aligned Dipole Moieties for Biomimetic Regulable Ion Transport.

Biological ion channels are renowned for their exceptional ion transport selectivity and adaptability to environmental changes, posing a significant challenge for synthetic mimicry. Herein, an innovative covalent–organic‐framework membrane featuring aligned benzothiadiazole units within its oriented 1D nanochannels is reported. These densely arrayed dipolar benzothiadiazole units enhance selective ion adsorption and facilitate membrane charge regulation. Consequently, the membrane can dynamically adjust its permselectivity toward ions, transitioning seamlessly between cation‐selective, ambipolar, and anion‐selective states. This versatility affects both the type of ions transported and the transport efficiency, supporting reversible and controlled membrane operation, as illustrated by the capacity to regulate the magnitude and direction of osmotic power. When interacting with multivalent anions, highly negatively charged channels of the membrane exhibit outstanding cation permselectivity and conductivity. Specifically, upon exposure to PO43− ions, the membrane achieves a remarkable osmotic power of 155 W m−2 and an energy conversion efficiency of 46.1% under salinity gradients of 0.5 and 0.01 m NaCl. Notably, introducing multivalent cations can reverse the polarity of the membrane. This work underscores the potential of exploiting ion‐dipolar interactions for the development of adaptive, ion‐selective membranes with promising applications in electrochemical sensing, energy conversion, and more. [ABSTRACT FROM AUTHOR]