A porous molecular crystal (PMC) assembled by close-packing of macrocyclic cyclotetrabenzoin acetate is an efficient adsorbent for selective CO<sub>2</sub> capture. The 7.1´7.1 Å square pore of PMC and its ester C=O group play important roles in improving its affinity for CO<sub>2</sub> molecules. Thermodynamically, the benzene walls of macrocycle strongly promote CO<sub>2</sub> adsorption via [p···p] interactions at low pressure. In addition, the polar carbonyl groups pointing inward the square channels reduce the size of aperture to a 5.0´5.0 Å square, which offers kinetic selectivity for CO<sub>2</sub> capture. The PMC features water tolerance and high structural stability under vacuum and various gas adsorption conditions, which are rare among intrinsically porous organic molecules. In mixed-gas breakthrough experiments, it exhibits efficient CO<sub>2</sub>/N<sub>2</sub> and CO<sub>2</sub>/CH<sub>4</sub> separations under kinetic flow conditions. Most importantly, the moderate adsorbate–adsorbent interaction allows the PMC to be readily regenerated, and therefore applied to pressure swing adsorption (PSA) processes. The eluted N<sub>2</sub> and CH<sub>4</sub> are obtained with over 99.9% and 99.8% purity, respectively, and the separation performance is stable for 30 cycles. Coupled with its easy synthesis, these properties make cyclotetrabenzoin acetate a promising adsorbent for CO<sub>2</sub> separations from flue and natural gases.
Hyperaging Tuning of a Carbon Molecular‐Sieve Hollow Fiber Membrane with Extraordinary Gas‐Separation Performance and Stability
