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The purification of p‐xylene (pX) from its xylene isomers represents a challenging but important industrial process. Herein, we report the efficient separation of pX from its ortho‐ and meta‐ isomers by a microporous calcium‐based metal–organic framework material (HIAM‐203) with a flexible skeleton. At 30 °C, all three isomers are accommodated but the adsorption kinetics of o‐xylene (oX) and m‐xylene (mX) are substantially slower than that of pX, and at an elevated temperature of 120 °C, oX and mX are fully excluded while pX can be adsorbed. Multicomponent column breakthrough measurements and vapor‐phase/liquid‐phase adsorption experiments have demonstrated the capability of HIAM‐203 for efficient separation of xylene isomers. Ab initio calculations have provided useful information for understanding the adsorption mechanism. [ABSTRACT FROM AUTHOR]

The purification of p‐xylene (pX) from its xylene isomers represents a challenging but important industrial process. Herein, we report the efficient separation of pX from its ortho‐ and meta‐ isomers by a microporous calcium‐based metal–organic framework material (HIAM‐203) with a flexible skeleton. At 30 °C, all three isomers are accommodated but the adsorption kinetics of o‐xylene (oX) and m‐xylene (mX) are substantially slower than that of pX, and at an elevated temperature of 120 °C, oX and mX are fully excluded while pX can be adsorbed. Multicomponent column breakthrough measurements and vapor‐phase/liquid‐phase adsorption experiments have demonstrated the capability of HIAM‐203 for efficient separation of xylene isomers. Ab initio calculations have provided useful information for understanding the adsorption mechanism. [ABSTRACT FROM AUTHOR]

The separation of alkane isomers is an important yet challenging process in the petrochemical industry. Being a crucial step to produce premium gasoline components as well as optimum ethylene feed, the current industrial separation by distillation is extremely energy intensive. Adsorptive separation based on zeolite is limited by insufficient adsorption capacity. Metal‐organic frameworks (MOFs) hold enormous promise as alternative adsorbents due to their diverse structural tunability and exceptional porosity. Precise control of their pore geometry/dimensions has led to superior performance. In this minireview, we highlight the recent progresses in developing MOFs for the separation of C6 alkane isomers. Representative MOFs are reviewed based on their separation mechanisms. Emphasis is put on the material design rationale for achieving optimal separation capability. Finally, we briefly discuss the existing challenges, possible solutions, and future directions of this important field. [ABSTRACT FROM AUTHOR]

The separation of alkane isomers is an important yet challenging process in the petrochemical industry. Being a crucial step to produce premium gasoline components as well as optimum ethylene feed, the current industrial separation by distillation is extremely energy intensive. Adsorptive separation based on zeolite is limited by insufficient adsorption capacity. Metal‐organic frameworks (MOFs) hold enormous promise as alternative adsorbents due to their diverse structural tunability and exceptional porosity. Precise control of their pore geometry/dimensions has led to superior performance. In this minireview, we highlight the recent progresses in developing MOFs for the separation of C6 alkane isomers. Representative MOFs are reviewed based on their separation mechanisms. Emphasis is put on the material design rationale for achieving optimal separation capability. Finally, we briefly discuss the existing challenges, possible solutions, and future directions of this important field. [ABSTRACT FROM AUTHOR]

High‐efficiency separation of C6 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 (H3tcpt=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 C6 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. [ABSTRACT FROM AUTHOR]

High‐efficiency separation of C6 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 (H3tcpt=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 C6 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. [ABSTRACT FROM AUTHOR]

[Display omitted] • A comprehensive study of naphtha separation by a series of adsorbents. • Influence of pore structure on the separation of real naphtha mixtures. • Influence of separation mechanism on the separation of naphtha mixtures. Naphtha separation is of significant importance for refineries to make full use of oil and to reduce the cost of refining. In the recent years, scientists have devoted great efforts to developing novel porous materials such as metal-organic frameworks (MOFs) for the separation of naphtha. However, previous investigations have been limited to single-component or 3- to 5-component model systems. Separation of full range hydrocarbon mixture such as naphtha has rarely been explored. In this work, we carry out a comprehensive study on the separation of alkane isomers as well as full range naphtha mixture by a series of robust microporous MOFs, e.g., Zr-abtc, Al-bttotb, Co-fa, in comparison with representative zeolite materials, e.g., ZSM-5 and zeolite 5A. We find that Al-bttotb and Co-fa, which can separate monobranched and dibranched alkanes through complete molecular exclusion, show superior separation performance for naphtha mixtures. This work may shed light on strategies for developing adsorbents with optimal performance for naphtha separation and ultimately realizing the industrialization of MOF-based separation technologies. [ABSTRACT FROM AUTHOR]

[Display omitted] • Downsizing a benchmark MOF into uniform nanosized materials. • Enhanced gas adsorption rate and capacity. • High-performance separation of propane and propylene. The separation of propane/propylene mixtures to produce polymer-grade propylene represents an important yet challenging task in the petrochemical industry. Metal-organic frameworks (MOFs) hold particular promise for the energy-efficient adsorptive separation of propane/propylene, in light of their structural diversity as well as highly tunable pore dimensions. MOFs exhibiting selective molecular exclusion for propylene over propane render exceptionally high adsorption selectivity. However, the relatively low adsorption capacity and/or slow diffusion kinetics have largely limited their separation efficiency. Here we report the fabrication of nano-sized crystals of a MOF-based splitter for propane and propylene. Compared to the micro-sized MOF samples, the nanocrystals display enhanced adsorption kinetics as well as notably improved adsorption capacity, making a new record with the highest efficiency for the separation of propane/propylene among all reported MOF-based splitters. Our study may shed light on the development of MOF-based adsorbents with optimal efficiency for industrially challenging gas separations. [ABSTRACT FROM AUTHOR]

• The large-scale synthesis of H 4 abtc (180 g scale) and Y-abtc (100 g scale) in high yields. • Breakthrough experiments on binary mixtures of propane/propylene at the 100 g scale. • Polymer grade propylene purity achieved using Y-abtc at 100 g scale. • Retained performance of Y-abtc at large scale demonstrating its potential for real world applications. Olefin/Paraffin separation, especially propylene purification from propane, is of extreme commercial importance as it produces chemical feedstock for synthetic plastics such as polypropylene. As an alternative to cryogenic distillation commonly used to purify these mixtures, the use of solid porous materials for adsorptive separation offers a more energetically efficient route. Metal-Organic Frameworks (MOFs) have shown great promise as adsorptive separation candidates in recent years. However, reports of these materials for the purification of C3 hydrocarbons exclusively provide insight of their performance in small scale laboratory settings. Single component isotherms and breakthrough curves are typically tested in the milligrams to gram scale. Herein, we present a scale-up, one-pot synthesis of a robust MOF with high propylene/propane selectivity. The organic linker 3,3′,5,5′-azobenzene-tetracarboxylic acid (H 4 abtc) and its yttrium-based MOF, Y-abtc, are both synthesized at the hundred-gram scale. Furthermore, we perform large-scale breakthrough experiments at the same scale. Our results show that Y-abtc samples synthesized from the one-pot 100 g scale reactions retain high crystallinity and size-exclusion based mechanism for the separation of propane/propylene mixtures. The same polymer-grade purity of propylene (>99.5%) is achieved as in the case of small scale (∼1 g) experiments. [ABSTRACT FROM AUTHOR]

Developing new techniques and materials for ethylene (C 2 H 4) and ethane (C 2 H 6) separation is an industrially significant but challenging task. Here we report two isoreticular pillar-layer metal-organic frameworks, Co(aip)(bpy) 0.5 and Co(aip)(pyz) 0.5 , for the separation of C 2 H 4 /C 2 H 6. The pore apertures of the pillar-layer metal-organic frameworks are rationally controlled by changing the length of the pillar ligands. Significantly, Co(aip)(pyz) 0.5 with a shorter pillar ligand shows reduced pore size and molecular sieving separation of C 2 H 4 from C 2 H 6. Co(aip)(pyz) 0.5 has a moderate C 2 H 4 capacity of 1.78 mmol/g but ultrahigh C 2 H 4 /C 2 H 6 selectivity exceeding 2000 at ambient conditions. The molecular simulation revealed that large torsion angle between the organic linker plane and Co–O bond leads to the high energy barrier for C 2 H 6 to enter into the pore, which results in the molecular sieving separation of C 2 H 4 /C 2 H 6. Dynamic breakthrough experiments confirmed the high selectivity of Co(aip)(pyz) 0.5 for C 2 H 4. And high-purity C 2 H 4 (>97%) with a C 2 H 4 productivity of 19.1 l/kg can be obtained through the desorption process. Meanwhile, the excellent reusability and moisture stability endow it great potential for applications in adsorptive separation. [Display omitted] • The pore apertures of the pillar-layer MOFs are rationally controlled. • Co(aip)(pyz) 0.5 showed the molecular sieving separation of C 2 H 4 /C 2 H 6. [ABSTRACT FROM AUTHOR]

[Display omitted] • MOF-11 breaks the trade-off between uptake and selectivity for Xe/Kr separation. • MOF-11 has the highest Xe uptake of 4.05 mmol/g at 0.2 bar and 298 K. • MOF-11 has high Xe/Kr Henry and IAST selectivity of 13.6 and 16.1 at 298 K. • Xe/Kr separation is achieved by the synergy between optimal pore size and OMSs. Efficient separation of Xenon (Xe) and krypton (Kr) is important in the gas industries but remains challenging. Adsorptive separation affords an energy-efficient method to isolate the two noble gases, yet developing selective adsorbents with high uptake and excellent selectivity remains difficult, limited by a trade-off between uptake and selectivity. We report MOF-11 with optimal pore size and accessible open metal sites (OMSs) for separation of Xe over Kr via the discriminable difference in van der Waals interactions. MOF-11 affords a new benchmark for Xe/Kr separation with high Xe uptakes of 4.05 and 4.95 mmol/g (at 0.2 and 1 bar), high Xe/Kr Henry and IAST selectivity (13.6 and 16.1) at 298 K. Evidenced by Xe-loaded structure, multiple Xe···H interactions between Xe and the terminal H atoms allow Xe atoms firmly packed within the framework. This work demonstrates a strategy for balancing uptake and selectivity in Xe/Kr separation by capitalizing on the synergy between optimal pore size and OMSs. [ABSTRACT FROM AUTHOR]