Expanding Linker Dimensionality in Metal‐organic Frameworks for sub‐Ångstrom Pore Control for Separation Applications

Macreadie, Lauren K.; Idrees, Karam B.; Smoljan, Courtney S.; Farha, Omar K.

doi:10.1002/anie.202304094

Cited by 19 publications

(12 citation statements)

References 68 publications

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“…The incorporation of 3D linkers in MOFs can dramatically alter the pore environment of the framework owing to the symmetrical core of the 3D linker. This results in a more uniform pore environment across the unit cell due to the consistent protrusion of 3D linkers into each pore . This effect is further amplified with higher symmetry 3D linkers such as p CDC, which offer a quasi-spherical icosahedral moiety that consistently protrudes into the pore in contrast to the BODC linker, which only has a threefold symmetry.…”

Section: Introductionmentioning

confidence: 99%

Robust Carborane-Based Metal–Organic Frameworks for Hexane Separation

Idrees,

Kirlikovali,

Setter

et al. 2023

J. Am. Chem. Soc.

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Hexane isomers play a vital role as feedstocks and fuel additives in the petrochemical industry. However, their similar physical and chemical properties lead to significant challenges in the separation process. Traditional thermal separation techniques are energy-intensive and lead to significant carbon footprint penalties. As such, there is a growing demand for the development of less energy-intensive nonthermal separation methods. Adsorption-based separation methods, such as using solid sorbents or membranes, have emerged as promising alternatives to distillation. Here, we report the successful synthesis of two novel metal–organic frameworks (MOFs), NU-2004 and NU-2005, by incorporating a carborane-based three-dimensional (3D) linker and using aluminum and vanadium nodes, respectively. These MOFs exhibit exceptional thermal stability and structural rigidity compared to other MIL-53 analogues, which is further corroborated using synchrotron studies. Furthermore, the inclusion of the quasi-spherical 3D linker in NU-2004 demonstrates significant advancements in the separation of hexane isomers compared to other MIL MOFs containing two-dimensional (2D) and aliphatic 3D linkers.

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Section: Introductionmentioning

confidence: 99%

Robust Carborane-Based Metal–Organic Frameworks for Hexane Separation

Idrees,

Kirlikovali,

Setter

et al. 2023

J. Am. Chem. Soc.

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“…Nevertheless, some hydrocarbon cages have been successfully incorporated into the backbones of oligomers and high polymers, − as well as into networked materials, where their rigidity imparts favorable stability and introduces new functional properties. − For example, Schlüter showed that the central inverted C–C bond in bicyclo[1.1.1]pentane could be polymerized to access high molecular weight poly([1.1.1]propellane)s ( A , Figure b) when a solubilizing substituent was present on the precursor cage. , Ishizone reported the synthesis of soluble poly(1,3-adamantanes)s ( B ) by cationic ring-opening polymerization of substituted 1,3-dehydroadamantanes. , In contrast, Reinhardt’s previous synthesis of unsubstituted polyadamantane by Wurtz coupling of dibromominated adamantane had yielded insoluble material that was only amenable to solid-state analytical techniques . Eaton reported the synthesis of poly(cubane)s ( C ), but only low molecular weight materials were accessible as each monomer unit was added in a separate reaction step and solubility challenges were encountered .…”

Section: Introductionmentioning

confidence: 99%

Three-Dimensional Synthons for Cage-Dense Inorganic Polymers and Materials

Bedard,

Chitnis

2023

Chem. Mater.

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The relationship between the monomer structure and polymer properties is central to materials science. Here we discuss the notion of monomer dimensionality, as it refers to the presence of 1-dimensional chains, 2-dimensional rings, or 3-dimensional cages in inorganic polymers. We first highlight ring-containing systems, followed by classical 3-dimensional inorganic monomers (carboranes and polyhedral oligomeric silsesquioxanes, POSS). We then outline our development of modularly accessible phosphorus− nitrogen (PN) cages into polymerizable synthons to access linear or networked inorganic materials. Finally, we summarize the most important obstacles to advancement in the field and point toward areas where the most impactful discoveries are expected. Throughout the Perspective, an emphasis is placed on the properties that emerge when three-dimensional inorganic cages are present in the main chain, particularly as they contrast with materials containing monomers of lower dimensionality.

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“…Metal–organic frameworks (MOFs) are among the most promising materials for advancing the utilization of adsorbent-based separations. Because of their regular structures and high designability, − pore sizes and host–guest interactions, which determine the gas selectivity and amount adsorbed, can be controlled by customizing the combination of metal ions , and organic ligands, , making it possible to prepare appropriate MOFs for specific separation systems. , In addition, several MOFs possess structural flexibility and exhibit structural deformation in response to external stimuli, such as temperature and pressure changes and light exposure. One notable manifestation of these is the adsorption-induced structural transition, commonly referred to as “gate opening” or “breathing,” which sharply increases the amount adsorbed at a threshold gas pressure (gate pressure). − This abrupt change in adsorption renders flexible MOFs useful in various industrial applications.…”

Section: Introductionmentioning

confidence: 99%

“…Metal−organic frameworks (MOFs) are among the most promising materials for advancing the utilization of adsorbentbased separations. Because of their regular structures and high designability, 3−8 pore sizes and host−guest interactions, which determine the gas selectivity and amount adsorbed, can be controlled by customizing the combination of metal ions 9,10 and organic ligands, 11,12 making it possible to prepare appropriate MOFs for specific separation systems. 13,14 In addition, several MOFs possess structural flexibility and exhibit structural deformation in response to external stimuli, such as temperature and pressure changes and light exposure.…”

Section: Introductionmentioning

confidence: 99%

Validating the Mechanism Underlying the Slacking of the Gate-Opening Behavior in Flexible Metal–Organic Frameworks Arising from the Application of External Force

Arima

Hiraide

Miyahara

et al. 2023

ACS Appl. Mater. Interfaces

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Flexible metal−organic frameworks (MOFs) are innovative adsorbents expected to revolutionize conventional separation systems as they exhibit stepwise adsorption arising from structural transitions, commonly known as "gate opening." However, because MOFs are typically obtained in powder form, they require shaping for industrial applications. In our previous study, we reported that the stepwise uptake observed in the CO 2 gate opening of ) 2 (4,4′-bipyridine) 2 ]) became less distinct when molded with polymer binders and found that this slacking phenomenon could be caused by the polymer binder inhibiting the structural change of the ELM-11 particles. In this study, we aimed to fully validate and generalize the mechanism behind the slacking of gate adsorption from both theoretical and experimental perspectives. First, we conducted grand canonical molecular dynamics simulations for a simplified MOF model to directly calculate free energy profiles of the particle to validate the slacking theory without any assumptions. The results confirmed the fundamental assumption made in our previous study that the deformation of the flexible motifs within the MOF particles occurs sequentially, which is a key factor contributing to the slacking phenomenon. The second part of the study focused on the relationship between the volume expansion ratio of MOFs and the degree of slacking. The relationship predicted by the theory was experimentally validated by comparing ELM-11, which exhibits 30% volume expansion, to another MOF with a mutually interpenetrating jungle-gym structure, which exhibits 10% volume expansion. These findings strengthened and generalized the understanding of the mechanism underlying the slacking of gate adsorption induced upon the application of external force, which could guide the fabrication of molded MOFs while maintaining a high adsorption efficiency for various industrial applications.

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Expanding Linker Dimensionality in Metal‐organic Frameworks for sub‐Ångstrom Pore Control for Separation Applications

Cited by 19 publications

References 68 publications

Robust Carborane-Based Metal–Organic Frameworks for Hexane Separation

Robust Carborane-Based Metal–Organic Frameworks for Hexane Separation

Three-Dimensional Synthons for Cage-Dense Inorganic Polymers and Materials

Validating the Mechanism Underlying the Slacking of the Gate-Opening Behavior in Flexible Metal–Organic Frameworks Arising from the Application of External Force

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