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Ethane/Ethylene Separations in Flexible Diamondoid Coordination Networks via an Ethane-Induced Gate-Opening Mechanism

Shaomin Wang, Mohana Shivanna, Su‐Tao Zheng, Tony Pham, Katherine A. Forrest, Qing‐Yuan Yang, Qingqing Guan, Brian Space, Susumu Kitagawa, Michael J. Zaworotko

2024Journal of the American Chemical Society109 citationsDOIOpen Access PDF

Abstract

Separating ethane (C 2 H 6 ) from ethylene (C 2 H 4 ) is an essential and energy-intensive process in the chemical industry. Here, we report two flexible diamondoid coordination networks, X-dia-1-Ni and X-dia-1-Ni 0.89 Co 0.11, that exhibit gate-opening between narrow-pore (NP) and large-pore (LP) phases for C 2 H 6, but not for C 2 H 4 . X-dia-1-Ni 0.89 Co 0.11 thereby exhibited a type F–IV isotherm at 273 K with no C 2 H 6 uptake and a high uptake (111 cm 3 g –1, 1 atm) for the NP and LP phases, respectively. Conversely, the LP phase exhibited a low uptake of C 2 H 4 (12.2 cm 3 g –1 ). This C 2 H 6 /C 2 H 4 uptake ratio of 9.1 for X-dia-1-Ni 0.89 Co 0.11 far surpassed those of previously reported physisorbents, many of which are C 2 H 4 -selective. In situ variable-pressure X-ray diffraction and modeling studies provided insight into the abrupt C 2 H 6 -induced structural NP to LP transformation. The promise of pure gas isotherms and, more generally, flexible coordination networks for gas separations was validated by dynamic breakthrough studies, which afforded high-purity (99.9%) C 2 H 4 in one step.

Topics & Concepts

DiamondoidChemistryMechanism (biology)EthyleneNanotechnologyOrganic chemistryMoleculeCatalysisEpistemologyMaterials sciencePhilosophyMetal-Organic Frameworks: Synthesis and ApplicationsCovalent Organic Framework ApplicationsMembrane Separation and Gas Transport