Group 3 Elements and Lanthanide Metals

Müller‐Buschbaum, Klaus

doi:10.1002/9783527693078.ch9

Cited by 6 publications

(6 citation statements)

References 196 publications

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“…Compared to the transition metals more commonly applied for MOF synthesis, the design of Ln-MOFs is more complex due to the high and variable coordination numbers (CN) of the trivalent lanthanide ions. On the other hand, the flexible coordination geometry hampers the prediction and control of the synthesized Ln-MOF structures; however, on the other hand, it opens the option to synthesize unusual and new architectures. − With the same lanthanide and organic linker, it is possible to realize distinct crystal structures . Since the pioneering synthesis by Reineke et al, Ln-MOF syntheses with BDC and derivatives reported structures crystallizing mostly in monoclinic and triclinic space groups.…”

Section: Introductionmentioning

confidence: 99%

Halogenated Terephthalic Acid “Antenna Effects” in Lanthanide-SURMOF Thin Films

Santos

Pramudya

Krstić

et al. 2020

ACS Appl. Mater. Interfaces

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Lanthanide-based crystalline coatings have a great potential for energy-conversion devices, but until now luminescent surface-anchored materials were difficult to fabricate. Thin films, called lanthanides surface-mounted metal–organic frameworks (SURMOFs) with tetrasubstituted halide (fluorine, chlorine, and bromine) terephthalic acid derivative linkers as a basic platform for optical devices, exhibit a high quantum yield of fluorescence visible to the naked eyes under ambient light. We show that we can tune the luminescent properties in thin films by halide substitution, which affords control over the molecular structure of the material. We rationalize the mechanism for the modulation of the photophysical properties by “antenna effect”, which controls the energy transfer and quantum yields using experimental and theoretical techniques for chelated lanthanides as a function of the type of atom substitutions at the phenyl rings and the resulting dihedral angle between phenyl rings in the linkers and carboxylate groups.

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Section: Introductionmentioning

confidence: 99%

Halogenated Terephthalic Acid “Antenna Effects” in Lanthanide-SURMOF Thin Films

Santos

Pramudya

Krstić

et al. 2020

ACS Appl. Mater. Interfaces

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“…Metal–organic frameworks (MOFs) are crystalline materials that are formed by the linkage of inorganic and organic units via strong bonds resulting in porous structures . Based on the principles of reticular chemistry, MOFs are designed by the appropriate choice of inorganic and organic building units, with well-defined geometrical features, to produce structures with targeted topologies. , For those MOFs constructed from lanthanide-based inorganic clusters linked by multicarboxylic acid linkers, an extensive number of different three-dimensional (3D) networks have been reported . This is primarily due to the high variability in coordination environment of lanthanide cations.…”

Section: Introductionmentioning

confidence: 99%

“…This is primarily due to the high variability in coordination environment of lanthanide cations. The use of Ln-based building units in the construction of new MOFs is attractive though because Ln cations typically have a high density of coordinated solvent ligands, which, when removed, can produce unsaturated metal sites that serve as gas binding or Lewis acidic sites . Moreover, hydroxyl ligands derived from water molecules binding to metal clusters have been exploited for their Lewis and/or Brønsted acidity in catalytic reactions. , Therefore, lanthanide-based metal–organic frameworks (Ln-MOFs) are promising candidates for the applications of gas capture − and heterogeneous acid-catalyzed reactions. − …”

Section: Introductionmentioning

confidence: 99%

“…1,2 For those MOFs constructed from lanthanide-based inorganic clusters linked by multicarboxylic acid linkers, an extensive number of different three-dimensional (3D) networks have been reported. 3 This is primarily due to the high variability in coordination environment of lanthanide cations. The use of Ln-based building units in the construction of new MOFs is attractive though because Ln cations typically have a high density of coordinated solvent ligands, which, when removed, can produce unsaturated metal sites that serve as gas binding or Lewis acidic sites.…”

Section: ■ Introductionmentioning

confidence: 99%

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A Series of Metal–Organic Frameworks for Selective CO₂ Capture and Catalytic Oxidative Carboxylation of Olefins

et al. 2018

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Three new lanthanide-based metal–organic frameworks (Ln-MOFs), namely MOF-590, -591, and -592 constructed from a tetratopic linker, benzoimidephenanthroline tetracarboxylic acid (H4BIPA-TC), were synthesized under solvothermal conditions and fully characterized. All of the new MOFs exhibit three-dimensional frameworks, which adopt unprecedented topologies in MOF field. Gas adsorption measurements of MOF-591 and -592 revealed good adsorption of CO2 (low pressure, at room temperature) and moderate CO2 selectivity over N2 and CH4. Consequently, breakthrough experiments illustrated the separation of CO2 from binary mixture of CO2 and N2 with the use of MOF-592. Accordingly, MOF-592 revealed the selective CO2 capture effectively without any loss in performance after three cycles. Moreover, MOF-590, -591, and -592 showed to be catalytically active in the oxidative carboxylation of styrene and CO2 for a one-pot synthesis of styrene carbonate under mild conditions (1 atm CO2, 80 °C, and without solvent). Among the new materials, MOF-590 revealed a remarkable efficiency with exceptional conversion (96%), selectivity (95%), and yield (91%).

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“…This results in high coordinative demand and brings out a high coordination number and connectivity, which facilitates the formation of stable 3D networks. 41 According to the best of our available knowledge, MOF-76(Y) was used for the very first time as filler in Matrimid polymer to fabricate MMMs. Gas permeation experiments under different conditions were conducted using pure and mixed gas compositions of CO 2 , CH 4 , and N 2 .…”

Section: Introductionmentioning

confidence: 99%

Synergistic solution of CO₂ capture by novel lanthanide-based MOF-76 yttrium nanocrystals in mixed-matrix membranes

Bano

Tariq

Ilyas

et al. 2019

Energy & Environment

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A porous and thermally stable metal organic framework (MOF) of yttrium and 1,3,5-benzenetricarboxylate was synthesized, which belongs to the family of lanthanide-based MOF-76. Mixed-matrix membranes were developed by incorporating MOF-76 yttrium nanocrystals into Matrimid® 5218. The structure, composition, and morphology of synthesized lanthanide-based MOF-76 yttrium nanocrystals and mixed-matrix membranes were characterized by X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, and thermogravimetric analysis. The characterizations and gas permeation results of the prepared mixed-matrix membranes confirmed better adhesion and distribution of filler particles in the polymer. The results demonstrated that the addition of MOF-76 yttrium nanocrystals to the polymer matrix improved both the gas selectivity and permeability of mixed-matrix membranes compared to pure Matrimid membranes. Permeability of CO2 increased from 7.24 to 27.29 Barrer by increasing the particle content from 0 to 30% in pure gas experiments. Whereas with 30 wt% concentration of MOF-76(Y) at 50:50 feed compositions, the selectivity increased for CO2/CH4 and CO2/N2 was 67% and 68%, respectively. The rise in temperature from 298 to 338 K decreased the ideal selectivity up to 25% for both gas pairs due to polymer chain relaxations at elevated temperatures. The commercial importance of membranes was evaluated at different feed compositions and operating temperatures.

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Group 3 Elements and Lanthanide Metals

Abstract: Scheme 9.1 Ln-MOFs and the multifunctionality of relevant properties.

Cited by 6 publications

References 196 publications

Halogenated Terephthalic Acid “Antenna Effects” in Lanthanide-SURMOF Thin Films

Halogenated Terephthalic Acid “Antenna Effects” in Lanthanide-SURMOF Thin Films

A Series of Metal–Organic Frameworks for Selective CO₂ Capture and Catalytic Oxidative Carboxylation of Olefins

Synergistic solution of CO₂ capture by novel lanthanide-based MOF-76 yttrium nanocrystals in mixed-matrix membranes

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Group 3 Elements and Lanthanide Metals

Abstract: Scheme 9.1 Ln-MOFs and the multifunctionality of relevant properties.

Cited by 6 publications

References 196 publications

Halogenated Terephthalic Acid “Antenna Effects” in Lanthanide-SURMOF Thin Films

Halogenated Terephthalic Acid “Antenna Effects” in Lanthanide-SURMOF Thin Films

A Series of Metal–Organic Frameworks for Selective CO2 Capture and Catalytic Oxidative Carboxylation of Olefins

Synergistic solution of CO2 capture by novel lanthanide-based MOF-76 yttrium nanocrystals in mixed-matrix membranes

Contact Info

Product

Resources

About

A Series of Metal–Organic Frameworks for Selective CO₂ Capture and Catalytic Oxidative Carboxylation of Olefins

Synergistic solution of CO₂ capture by novel lanthanide-based MOF-76 yttrium nanocrystals in mixed-matrix membranes