Layered microporous polymers by solvent knitting method

Two-dimensional (2D) nanomaterials, especially 2D organic nanomaterials with unprecedentedly diverse and controlled structure, have attracted decent scientific interest. Among the preparation strategies, the top-down approach is one of the considered low-cost and scalable strategies to obtain 2D organic nanomaterials. However, some factors of their layered counterparts limited the development and potential applications of 2D organic nanomaterials, such as type, stability, and strict synthetic conditions of layered counterparts. We report a class of layered solvent knitting hyper-cross-linked microporous polymers (SHCPs) prepared by improving Friedel-Crafts reaction and using dichloroalkane as an economical solvent, stable electrophilic reagent, and external cross-linker at low temperature, which could be used as layered counterparts to obtain previously unknown 2D SHCP nanosheets by method of ultrasonic-assisted solvent exfoliation. This efficient and low-cost strategy can produce previously unreported microporous organic polymers with layered structure and high surface area and gas storage capacity. The pore structure and surface area of these polymers can be controlled by tuning the chain length of the solvent, the molar ratio of AlCl(3), and the size of monomers. Furthermore, we successfully obtain an unprecedentedly high–surface area HCP material (3002 m(2) g(−1)), which shows decent gas storage capacity (4.82 mmol g(−1) at 273 K and 1.00 bar for CO(2); 12.40 mmol g(−1) at 77.3 K and 1.13 bar for H(2)). This finding provides an opportunity for breaking the constraint of former knitting methods and opening up avenues for the design and synthesis of previously unknown layered HCP materials.