Abstract

    Developing porous materials with ultrahigh surface areas for gas storage (for example, methane) is attractive but challenging. Here, we report two isostructural three-dimensional covalent organic frameworks (COFs) with a rare self-catenated alb-3,6-Ccc2 topology and a pore size of 1.1 nanometer. Notably, these imine-linked microporous COFs show both high gravimetric Brunauer–Emmett–Teller (BET) surface areas (~4400 square meters per gram) and volumetric BET surface areas (~1900 square meters per cubic centimeter). Moreover, their volumetric methane uptake reaches up to 264 cubic centimeter (standard temperature and pressure) per cubic centimeter [cm3 (STP) cm−3] at 100 bar and 298 kelvin, and they exhibit the highest volumetric working capacity of 237 cm3 (STP) cm−3 at 5 to 100 bar and 298 kelvin among all reported porous crystalline materials.