High-efficiency separation of C alkanes, particularly the mono- and dibranched isomers by using porous solids, is of paramount significance in the petrochemical industry and, remains a daunting challenge. In this work, we report the complete separation of linear/monobranched hexanes from their dibranched isomers through selective size-exclusion by a microporous MOF, Zn-tcpt (H tcpt=2,4,6-tris(4-carboxyphenoxy)-1,3,5-triazine), with a two-fold interpenetrated structure of hms nets. Importantly, its adsorption capacity and selectivity are notably higher than those of the previously reported adsorbents that can split mono- and dibranched alkane isomers. Dynamic breakthrough measurements verify the excellent separation of C alkane isomers by Zn-tcpt, and the size-exclusion based separation mechanism has been confirmed by ab initio materials modeling. The high-efficiency separation of alkane isomers by Zn-tcpt can be attributed to its optimal pore dimensions as well as high porosity.
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http://dx.doi.org/10.1002/anie.202211359 | DOI Listing |
Chem Sci
December 2024
Key Laboratory of Biomass Chemical Engineering of the Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University 866 Yuhangtang Road Hangzhou 310058 China
J Am Chem Soc
June 2024
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, Zhejiang 310027, China.
Angew Chem Int Ed Engl
July 2024
College of Chemistry and Materials Science, Guangdong Provincial Key Laboratory of Functional Supramolecular Coordination Materials and Applications, Jinan University, Guangzhou, 510632, China.
Metal-organic frameworks (MOFs) that exhibit dynamic phase-transition behavior under external stimuli could have great potential in adsorptive separations. Here we report on a zinc-based microporous MOF (JNU-80) and its reversible transformation between two crystalline phases: large pore (JNU-80-LP) and narrow pore (JNU-80-NP). Specifically, JNU-80-LP can undergo a dehydration-induced cluster consolidation under heat treatment, resulting in JNU-80-NP with a reduced channel that allows exclusion of di-branched hexane isomers while high adsorption of linear and mono-branched hexane isomers.
View Article and Find Full Text PDFNat Commun
March 2024
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, China.
Extensive efforts have been made to improve the separation selectivity of hydrocarbon isomers with nearly distinguishable boiling points; however, how to balance the high regeneration energy consumption remains a daunting challenge. Here we describe the efficient separation of hexane isomers by constructing and exploiting the rotational freedom of organic linkers and inorganic SnF anions within adaptive frameworks, and reveal the nature of flexible host-guest interactions to maximize the gas-framework interactions while achieving potential energy storage. This approach enables the discrimination of hexane isomers according to the degree of branching along with high capacity and record mono-/di-branched selectivity (6.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
April 2024
Institut des Matériaux Poreux de Paris, ESPCI Paris, Ecole Normale Supérieure, CNRS, PSL University, 75005, Paris, France.
The improvement of the Total Isomerization Process (TIP) for the production of high-quality gasoline with the ultimate goal of reaching a Research Octane Number (RON) higher than 92 requires the use of specific sorbents to separate pentane and hexane isomers into classes of linear, mono- and di-branched isomers. Herein we report the design of a new multi-cage microporous Fe(III)-MOF (referred to as MIP-214, MIP stands for materials of the Institute of Porous Materials of Paris) with a flu-e topology, incorporating an asymmetric heterofunctional ditopic ligand, 4-pyrazolecarboxylic acid, that exhibits an appropriate microporous structure for a thermodynamic-controlled separation of hydrocarbon isomers. This MOF produced via a direct, scalable, and mild synthesis route was proven to encompass a unique separation of C5/C6 isomers by classes of low RON over high RON alkanes with a sorption hierarchy: (n-hexane≫n-pentane≈2-methylpentane>3-methylpentane)≫(2,3-dimethylbutane≈i-pentane≈2,2-dimethylbutane) following the adsorption enthalpy sequence.
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