Tuning the Structures of Metal–Organic Frameworks <i>via</i> a Mixed-Linker Strategy for Ethylene/Ethane Kinetic Separation

Lyndon, Richelle; You, Wenqin; Ma, Yao; Bacsa, John; Gong, Yutao; Stangland, Eric E.; Walton, Krista S.; Sholl, David S.; Lively, Ryan P.

doi:10.1021/acs.chemmater.9b04177

Cited by 54 publications

(34 citation statements)

References 62 publications

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“…KD is a concept that has been widely used to represent the molecular size in the field of molecular sieving [30][31][32] . Our work, however, provides an example that this static view of molecular size fails to capture the flexible nature of molecules in entering a tight space.…”

Section: Discussionmentioning

confidence: 99%

Selective filling of n-hexane in a tight nanopore

Rayabharam

et al. 2021

Nat Commun

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Molecular sieving may occur when two molecules compete for a nanopore. In nearly all known examples, the nanopore is larger than the molecule that selectively enters the pore. Here, we experimentally demonstrate the ability of single-wall carbon nanotubes with a van der Waals pore size of 0.42 nm to separate n-hexane from cyclohexane—despite the fact that both molecules have kinetic diameters larger than the rigid nanopore. This unexpected finding challenges our current understanding of nanopore selectivity and how molecules may enter a tight channel. Ab initio molecular dynamics simulations reveal that n-hexane molecules stretch by nearly 11.2% inside the nanotube pore. Although at a relatively low probability (28.5% overall), the stretched state of n-hexane does exist in the bulk solution, allowing the molecule to enter the tight pore even at room temperature. These insights open up opportunities to engineer nanopore selectivity based on the molecular degrees of freedom.

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Section: Discussionmentioning

confidence: 99%

Selective filling of n-hexane in a tight nanopore

Rayabharam

et al. 2021

Nat Commun

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“…In all those structures, the intracrystalline diffusivity of propylene was one order of magnitude lower compared to that of propane. In a separate work, A mixed linker MOF consists of benzotriazole (BTA) and benzimidazole (BIM) as linkers and Zn metal centers with BTA/BIM ratio 4/1 demonstrated kinetic separation of ethane and ethylene (Lyndon et al, 2020). Kinetic separation has also been performed for propane/propylene separation by zeolite imidazolate framework (Li et al, 2009).…”

Section: Diffusion and Kinetics-based Separationmentioning

confidence: 99%

Elucidating the mechanisms of Paraffin-Olefin separations using nanoporous adsorbents: An overview

Saha

Kim²,

Robinson³

et al. 2021

iScience

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Light olefins are the precursors of all modern-day plastics. Olefin is always mixed with paraffins in the time of production, and therefore it needs to be separated from paraffins to produce polymer-grade olefin. The state-of-the-art separation technique, cryogenic distillation, is highly expensive and hazardous. Adsorption could be a novel, sustainable, and inexpensive separation strategy, provided a suitable adsorbent can be designed. There are different types of mechanisms that were harnessed for the separation of olefins by adsorption, and in this review, we have focused our discussion on those mechanisms. These mechanisms include, (a) Affinity-based separation, like pi complexation and hydrogen bonding, (b) Separation based on pore size and shape, like size-exclusion and gate-opening effect, and (c) Non-equilibrium separation, like kinetic separation. In this review, we have elaborated each of the separation strategies from the fundamental level and explained their roles in the separation processes of different types of paraffins and olefins.

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“…However, the adsorption capacity is also limited by its contracted aperture. A robust MOF GT‐18 with optimum pore size and shape was synthesized through a mixed‐linker strategy and displayed promising diffusion selectivity toward ethylene [71] . With a benzotriazole (BTA)/benzimidazole (BIM) linker synthesis ratio of 4:1, GT‐18 was obtained, featuring a 10‐ring window and flexible pore apertures (≈3 Å).…”

Section: Olefin–paraffin Separationmentioning

confidence: 99%

Separation and Purification of Hydrocarbons with Porous Materials

Weckhuysen

2021

Angewandte Chemie

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is currently a postdoctoral researcher in Prof. Weckhuysen's group at Utrecht University. She received her PhD degree in Industrial Catalysis from the Dalian Institute of Chemical Physics, Chinese Academy of Sciences (2020) under the direction of Prof. Yunpeng Xu and Prof. Zhongmin Liu. Her current research interests include developing MOF thin films for ethene polymerization and gas adsorption. Bert M. Weckhuysen obtained his PhD degree from K. U. Leuven (Belgium) in 1995. After postdoctoral stays at Lehigh University (PA, USA) and Texas A&M University (TX, USA), he became full Professor at Utrecht University (The Netherlands) in 2000. His research focuses on the development and use of in situ and operando spectroscopy for studying solid catalysts under realistic reaction conditions at different length scales. Scheme 1. Timeline summarizing the trends in adsorptive hydrocarbon separation and purification with various porous materials over the latest three decades.

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Tuning the Structures of Metal–Organic Frameworks via a Mixed-Linker Strategy for Ethylene/Ethane Kinetic Separation

Cited by 54 publications

References 62 publications

Selective filling of n-hexane in a tight nanopore

Selective filling of n-hexane in a tight nanopore

Elucidating the mechanisms of Paraffin-Olefin separations using nanoporous adsorbents: An overview

Separation and Purification of Hydrocarbons with Porous Materials

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