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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author Guihong Xu
Tian Ke
Rongrong Fan
Kaiyuan Tan
Wenjun Zhang
Baogen Su
Zhiguo Zhang
Zongbi Bao
Qilong Ren
Qiwei Yang
author_facet Guihong Xu
Tian Ke
Rongrong Fan
Kaiyuan Tan
Wenjun Zhang
Baogen Su
Zhiguo Zhang
Zongbi Bao
Qilong Ren
Qiwei Yang
author_sort Guihong Xu
collection DOAJ
description 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.
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institution Kabale University
issn 2198-3844
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spelling doaj-art-3fb960000c134f86849293936a1dccf42025-01-29T09:50:19ZengWileyAdvanced Science2198-38442025-01-01124n/an/a10.1002/advs.202411083Divergent Adsorption Regulation in Metal–Organic Frameworks for Highly Efficient CF4/C2F6 SeparationGuihong Xu0Tian Ke1Rongrong Fan2Kaiyuan Tan3Wenjun Zhang4Baogen Su5Zhiguo Zhang6Zongbi Bao7Qilong Ren8Qiwei Yang9Key Laboratory of Biomass Chemical Engineering of Ministry of Education College of Chemical and Biological Engineering, Zhejiang University Hangzhou 310027 ChinaKey Laboratory of Biomass Chemical Engineering of Ministry of Education College of Chemical and Biological Engineering, Zhejiang University Hangzhou 310027 ChinaKey Laboratory of Biomass Chemical Engineering of Ministry of Education College of Chemical and Biological Engineering, Zhejiang University Hangzhou 310027 ChinaKey Laboratory of Biomass Chemical Engineering of Ministry of Education College of Chemical and Biological Engineering, Zhejiang University Hangzhou 310027 ChinaInstitute of Zhejiang University‐Quzhou Quzhou 324000 ChinaKey Laboratory of Biomass Chemical Engineering of Ministry of Education College of Chemical and Biological Engineering, Zhejiang University Hangzhou 310027 ChinaKey Laboratory of Biomass Chemical Engineering of Ministry of Education College of Chemical and Biological Engineering, Zhejiang University Hangzhou 310027 ChinaKey Laboratory of Biomass Chemical Engineering of Ministry of Education College of Chemical and Biological Engineering, Zhejiang University Hangzhou 310027 ChinaKey Laboratory of Biomass Chemical Engineering of Ministry of Education College of Chemical and Biological Engineering, Zhejiang University Hangzhou 310027 ChinaKey Laboratory of Biomass Chemical Engineering of Ministry of Education College of Chemical and Biological Engineering, Zhejiang University Hangzhou 310027 ChinaAbstract 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.https://doi.org/10.1002/advs.202411083adsorptiondivergent regulationgas separationmetal–organic frameworksperfluorocarbons
spellingShingle Guihong Xu
Tian Ke
Rongrong Fan
Kaiyuan Tan
Wenjun Zhang
Baogen Su
Zhiguo Zhang
Zongbi Bao
Qilong Ren
Qiwei Yang
Divergent Adsorption Regulation in Metal–Organic Frameworks for Highly Efficient CF4/C2F6 Separation
Advanced Science
adsorption
divergent regulation
gas separation
metal–organic frameworks
perfluorocarbons
title Divergent Adsorption Regulation in Metal–Organic Frameworks for Highly Efficient CF4/C2F6 Separation
title_full Divergent Adsorption Regulation in Metal–Organic Frameworks for Highly Efficient CF4/C2F6 Separation
title_fullStr Divergent Adsorption Regulation in Metal–Organic Frameworks for Highly Efficient CF4/C2F6 Separation
title_full_unstemmed Divergent Adsorption Regulation in Metal–Organic Frameworks for Highly Efficient CF4/C2F6 Separation
title_short Divergent Adsorption Regulation in Metal–Organic Frameworks for Highly Efficient CF4/C2F6 Separation
title_sort divergent adsorption regulation in metal organic frameworks for highly efficient cf4 c2f6 separation
topic adsorption
divergent regulation
gas separation
metal–organic frameworks
perfluorocarbons
url https://doi.org/10.1002/advs.202411083
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