Divergent Adsorption Regulation in Metal–Organic Frameworks for Highly Efficient CF4/C2F6 Separation

Abstract The efficient removal of low‐concentration components from homologous mixtures is often hampered by the co‐directional effect of traditional thermodynamic regulation approaches, typically leading to a trade‐off between adsorption capacity and selectivity. Focusing this challenge on the crit...

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Main Authors: Guihong Xu, Tian Ke, Rongrong Fan, Kaiyuan Tan, Wenjun Zhang, Baogen Su, Zhiguo Zhang, Zongbi Bao, Qilong Ren, Qiwei Yang
Format: Article
Language:English
Published: Wiley 2025-01-01
Series:Advanced Science
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Online Access:https://doi.org/10.1002/advs.202411083
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Summary:Abstract The efficient removal of low‐concentration components from homologous mixtures is often hampered by the co‐directional effect of traditional thermodynamic regulation approaches, typically leading to a trade‐off between adsorption capacity and selectivity. Focusing this challenge on the critical task of purifying perfluorocarbons in electronics industry, a divergent regulation strategy is reported that significantly improves the separation efficiency of low‐concentration hexafluoroethane (C2F6) from tetrafluoromethane (CF4). This approach involves the selective shielding of open metal sites and the modulation of channel geometry within an electron‐deficient ligand‐based pore environment, thereby facilitating a C2F6 dense‐packing accommodation mode while weakening the CF4 affinity due to the reduced host‐guest interactions. Simultaneously enhanced C2F6 adsorption and reduced CF4 adsorption are achieved, resulting in record‐high low‐pressure C2F6 uptake and C2F6/CF4 selectivity. Comprehensive insights into the unique separation mechanism are illustrated through a combination of solid‐state MAS nuclear magnetic resonance (SSNMR), molecular simulations, and meticulously designed comparative experiments. As a result, benchmark C2F6/CF4 separation performance is achieved, as demonstrated by the unprecedented electronic‐grade (over 99.999%) CF4 productivity (401 L kg−1) obtained from an industrially relevant C2F6/CF4 (3:97) mixture, as well as the excellent water/air/heat stability and recyclability.
ISSN:2198-3844