Superhigh and Robust Ion Selectivity in Membranes Assembled with Monolayer Clay Nanosheets

Abstract It is crucial to control the ion transport in membranes for various technological applications such as energy storage and conversion. The emerging functional two‐dimensional (2D) nanosheets such as graphene oxide and MXenes show great potential for constructing ordered nanochannels, but the assembled membranes suffer from low ion selectivity and stability. Here a class of robust charge‐selective membranes with superhigh cation/anion selectivity, which are assembled with monolayer nanosheets of cationic/anionic clays that inherently have permanent and uniform charges on each layer is reported. The transport number of cations/anions of cationic vermiculite nanosheet membranes (VNMs)/anionic Co‐Al layered double hydroxide (CoAl‐LDH) nanosheet membranes is over 0.90 in different NaCl concentration gradients, outperforming all the reported ion‐selective membranes. Importantly, this excellent ion selectivity can persist at high‐concentration salt solutions, under acidic and alkaline conditions, and for a wide range of ions of different sizes and charges. By coupling a pair of cation‐selective vermiculite membrane and anion‐selective CoAl‐LDH membrane, a reverse electrodialysis device which shows an output power density of 0.7 W m⁻² and energy conversion efficiency of 45.5% is constructed. This work provides a new strategy to rationally design high‐performance ion‐selective membranes by using 2D nanosheets with inherent surface charges for controllable ion‐transport applications.