ABSTRACT The separation of cyclohexane (Cy) and benzene (Bz) remains a long‐standing challenge in the chemical industry due to their nearly identical physicochemical properties. Conventional distillation methods are energy‐intensive and inefficient, particularly for removing unreacted Cy during Bz production via catalytic dehydrogenation. Developing porous materials capable of selectively adsorbing Cy offers an energy‐efficient alternative; however, such materials are rare. Herein, we present a calcium–organic framework, Ca‐MTTOB, constructed from Ca 2+ ions and a multitopic octacarboxylic acid linker (H 8 MTTOB), which forms rigid 1D pore channels. At 298 K, Ca‐MTTOB exhibits a saturated Cy adsorption capacity of 3.15 mmol g −1 and a Cy/Bz selectivity of 17.67. Breakthrough experiments demonstrate that Ca‐MTTOB preferentially adsorbs Cy under dynamic conditions. These results highlight Ca‐MTTOB as a high‐performance material for efficient and selective Cy/Bz separation, offering a promising route toward low‐energy benzene purification.
She et al. (2026) studied this question.