Nanoconfinement enabled non-covalently decorated MXene membranes for ion-sieving

Covalent modification is commonly used to tune the channel size and functionality of 2D membranes. However, common synthesis strategies used to produce such modifications are known to disrupt the structure of the membranes. Herein, we report less intrusive yet equally effective non-covalent modifications on Ti₃C₂T_x MXene membranes by a solvent treatment, where the channels are robustly decorated by protic solvents via hydrogen bond network. The densely functionalized (-O, -F, -OH) Ti₃C₂T_x channel allows multiple hydrogen bond establishment and its sub-1-nm size induces a nanoconfinement effect to greatly strengthen these interactions by maintaining solvent-MXene distance and solvent orientation. In sub-1-nm ion sieving and separation, as-decorated membranes exhibit stable ion rejection, and proton-cation (H⁺/Mⁿ⁺) selectivity that is up to 50 times and 30 times, respectively, higher than that of pristine membranes. It demonstrates the feasibility of non-covalent methods as a broad modification alternative for nanochannels integrated in energy-, resource- and environment-related applications.