Unusual adsorption behavior of volatile hydrocarbons on MOF-5 studied using thermodesorption methods

Makowski, Wacław; Mańko, Maria; Zabierowski, Piotr; Mlekodaj, Kinga; Majda, Dorota; Szklarzewicz, Janusz; Łasocha, Wiesław

doi:10.1016/j.tca.2014.04.016

Cited by 22 publications

(23 citation statements)

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“…We conclude that even materials with pore sizes on the order of nanometers can support vapor-liquid coexistence provided they possess the correct topology.T his provides an atural explanation for the anomalous behavior reported for benzene and related molecules in IRMOF-1. [6,7] More broadly,weanticipate that this phenomenon is not limited to vapor-liquid equilibria. Similar effects,f or example,c an be expected for liquid-liquid mixtures.T he ability to substantially tune the critical point of apure fluid sheds new light on av ery classic phenomenon, portending ar evisiting of pure and multicomponent phase behavior in nanoporous materials.…”

Section: Methodsmentioning

confidence: 95%

“…Previous NMR and molecular dynamics studies [6] of benzene motion in IRMOF-1yielded diffusivities associated with two domains of differing mobilities.Adsorption experiments showed features suggesting multiple surface energies. [7] Finally,g rand-canonical Monte Carlo simulations [8] detailed an arrow hysteresis loop for cyclohexane in IRMOF-1, which was reluctantly associated with capillary condensation even though the authors noted that the pores of IRMOF-1 are too small to support the effect. [3] In contrast, others proposed that the step in the CO 2 adsorption isotherm in IRMOF-1 is related to avapor-liquid transition.…”

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confidence: 99%

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Nanoporous Materials Can Tune the Critical Point of a Pure Substance

et al. 2015

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Molecular simulations and NMR relaxometry experiments demonstrate that pure benzene or xylene confined in isoreticular metal–organic frameworks (IRMOFs) exhibit true vapor–liquid phase equilibria where the effective critical point may be reduced by tuning the structure of the MOF. Our results are consistent with vapor and liquid phases extending over many MOF unit cells. These results are counterintuitive since the MOF pore diameters are approximately the same length scale as the adsorbate molecules. As applications of these materials in catalysis, separations, and gas storage rely on the ability to tune the properties of adsorbed molecules, we anticipate that the ability to systematically control the critical point, thereby preparing spatially inhomogeneous local adsorbate densities, could add a new design tool for MOF applications.

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Section: Methodsmentioning

confidence: 95%

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confidence: 99%

Nanoporous Materials Can Tune the Critical Point of a Pure Substance

et al. 2015

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“…At horough analysis of solvent-induced structural changesa nd the investigation of sorption properties of the tested materials were conducted by meanso fp owder X-ray diffraction, TGA, IR, dynamic vapor sorption, and quasi-equilibrated temperatureprogrammed desorption and adsorption (QE-TPDA). [39][40][41][42][43][44][45][46] Powder X-ray diffraction…”

Section: Investigation Of Scsc By Multiple Physical Techniquesmentioning

confidence: 99%

Guest‐Dependent Pressure‐Induced Spin Crossover in Fe^II₄[M^IV(CN)₈]₂ (M=Mo, W) Cluster‐Based Material Showing Persistent Solvent‐Driven Structural Transformations

Jankowski

Reczyński

Chorąży

et al. 2020

Chemistry A European J

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Discrete molecular species that can perform certain functions in response to multiple external stimuli constitute a special class of multifunctional molecular materials called smart molecules. Herein, cyanido‐bridged coordination clusters {[FeII(2‐pyrpy)2]4[MIV(CN)8]2}⋅4 MeOH⋅6 H2O (M=Mo (1 solv), M=W (2 solv) and 2‐pyrpy=2‐(1‐pyrazolyl)pyridine are presented, which show persistent solvent driven single‐crystal‐to‐single‐crystal transformations upon sorption/desorption of water and methanol molecules. Three full desolvation–resolvation cycles with the concomitant change of the host molecules do not damage the single crystals. More importantly, the Fe4M2 molecules constitute a unique example where the presence of the guests directly affects the pressure‐induced thermal spin crossover (SCO) phenomenon occurring at the FeII centres. The hydrated phases show a partial SCO with approximately two out‐of‐four FeII centres undergoing a gradual thermal SCO at 1 GPa, while in the anhydrous form the pressure‐induced SCO effect is almost quenched with only 15 % of the FeII centres undergoing high‐spin to low‐spin transition at 1 GPa.

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“…[6,7] More broadly,weanticipate that this phenomenon is not limited to vapor-liquid equilibria. Similar effects,f or example,c an be expected for liquid-liquid mixtures.T he ability to substantially tune the critical point of apure fluid sheds new light on av ery classic phenomenon, portending ar evisiting of pure and multicomponent phase behavior in nanoporous materials.…”

Section: Methodsmentioning

confidence: 95%

“…Previous NMR and molecular dynamics studies [6] of benzene motion in IRMOF1yielded diffusivities associated with two domains of differing mobilities.Adsorption experiments showed features suggesting multiple surface energies. [7] Finally,g rand-canonical Monte Carlo simulations [8] detailed an arrow hysteresis loop for cyclohexane in IRMOF-1, which was reluctantly associated with capillary condensation even though the authors noted that the pores of IRMOF-1 are too small to support the effect. [3] In contrast, others proposed that the step in the CO 2 adsorption isotherm in IRMOF-1 is related to avapor-liquid transition.…”

mentioning

confidence: 99%

Nanoporous Materials Can Tune the Critical Point of a Pure Substance

et al. 2015

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Molecular simulations and NMR relaxometry experiments demonstrate that pure benzene or xylene confined in isoreticular metal-organic frameworks (IRMOFs) exhibit true vapor-liquid phase equilibria where the effective critical point may be reduced by tuning the structure of the MOF.Our results are consistent with vapor and liquid phases extending over many MOF unit cells.T hese results are counterintuitive since the MOF pore diameters are approximately the same length scale as the adsorbate molecules.A sa pplications of these materials in catalysis,separations,and gas storage rely on the ability to tune the properties of adsorbed molecules,w e anticipate that the ability to systematically control the critical point, therebypreparing spatially inhomogeneous local adsorbate densities,c ould add an ew design tool for MOF applications.

show abstract

Unusual adsorption behavior of volatile hydrocarbons on MOF-5 studied using thermodesorption methods

Cited by 22 publications

References 31 publications

Nanoporous Materials Can Tune the Critical Point of a Pure Substance

Nanoporous Materials Can Tune the Critical Point of a Pure Substance

Guest‐Dependent Pressure‐Induced Spin Crossover in Fe^II₄[M^IV(CN)₈]₂ (M=Mo, W) Cluster‐Based Material Showing Persistent Solvent‐Driven Structural Transformations

Nanoporous Materials Can Tune the Critical Point of a Pure Substance

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Unusual adsorption behavior of volatile hydrocarbons on MOF-5 studied using thermodesorption methods

Cited by 22 publications

References 31 publications

Nanoporous Materials Can Tune the Critical Point of a Pure Substance

Nanoporous Materials Can Tune the Critical Point of a Pure Substance

Guest‐Dependent Pressure‐Induced Spin Crossover in FeII4[MIV(CN)8]2 (M=Mo, W) Cluster‐Based Material Showing Persistent Solvent‐Driven Structural Transformations

Nanoporous Materials Can Tune the Critical Point of a Pure Substance

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Guest‐Dependent Pressure‐Induced Spin Crossover in Fe^II₄[M^IV(CN)₈]₂ (M=Mo, W) Cluster‐Based Material Showing Persistent Solvent‐Driven Structural Transformations