Synthesis of Ionic Ultramicroporous Polymers for Selective Separation of Acetylene from Ethylene

Abstract The design of highly stable and efficient porous materials is essential for developing breakthrough hydrocarbon separation methods based on physisorption to replace currently used energy‐intensive distillation/absorption technologies. Efforts to develop advanced porous materials such as zeolites, coordination frameworks, and organic polymers have met with limited success. Here, a new class of ionic ultramicroporous polymers (IUPs) with high‐density inorganic anions and narrowly distributed ultramicroporosity is reported, which are synthesized by a facile free‐radical polymerization using branched and amphiphilic ionic compounds as reactive monomers. A covalent and ionic dual‐crosslinking strategy is proposed to manipulate the pore structure of amorphous polymers at the ultramicroporous scale. The IUPs exhibit exceptional selectivity (286.1–474.4) for separating acetylene from ethylene along with high thermal and water stability, collaboratively demonstrated by gas adsorption isotherms and experimental breakthrough curves. Modeling studies unveil the specific binding sites for acetylene capture as well as the interconnected ultramicroporosity for size sieving. The porosity‐engineering protocol used in this work can also be extended to the design of other ultramicroporous materials for the challenging separation of other key gas constituents.