Encapsulated Metallic Nanoparticles in Metal–Organic Frameworks: Toward Their Use in Catalysis

Leus, Karen; Jena, Himanshu Sekhar; Voort, Pascal Van Der

doi:10.1002/9783527809097.ch13

Cited by 2 publications

(2 citation statements)

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“…Significant efforts have been dedicated to distinguishing whether catalysis indeed takes place inside the pores or through fast leachingredeposition (boomerang) mechanisms. 40,41 It is essential that the reaction should take place inside the pores when the desired catalytic process is only feasible in confinement. When confinement is not strictly required, an alternative could be to use two-dimensional metal−organic layers or metal−organic nanosheets.…”

Section: ■ Introductionmentioning

confidence: 99%

Metal–Organic Frameworks as Catalysts for Organic Synthesis: A Critical Perspective

et al. 2019

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Recent advances in organic chemistry and materials chemistry have enabled the porosity of new materials to be accurately controlled on the nanometer scale. In this context, metal–organic frameworks (MOFs) have rapidly become one of the most attractive classes of solid supports currently under investigation in heterogeneous catalysis. Their unprecedented degree of tunability gives MOFs the chance to succeed where others have failed. The past decade has witnessed an exponential growth in the complexity of new structures. MOFs with a variety of topologies and pore sizes show excellent stability across wide ranges of pH and temperature. Even the controlled insertion of defects, to alter the MOF’s properties in a predictable manner, has become commonplace. However, research on catalysis with MOFs has been sluggish in catching up with modern trends in organic chemistry. Relevant issues such as enantioselective processes, C–H activation, or olefin metathesis are still rarely discussed. In this Perspective, we highlight meritorious examples that tackle important issues from contemporary organic synthesis, and that provide a fair comparison with existing catalysts. Some of these MOF catalysts already outcompete state-of-the-art homogeneous solutions. For others, improvements may still be required, but they have merit in aiming for the bigger challenge. Furthermore, we also identify some important areas where MOFs are likely to make a difference, by addressing currently unmet needs in catalysis instead of trying to outcompete homogeneous catalysts in areas where they excel. Finally, we strongly advocate for rational design of MOF catalysts, founded on a deep mechanistic understanding of the events taking place inside the pore.

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Section: ■ Introductionmentioning

confidence: 99%

Metal–Organic Frameworks as Catalysts for Organic Synthesis: A Critical Perspective

et al. 2019

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“…Metal–organic framework (MOFs) are crystalline nanoporous materials with a tunable structure and porosity. This makes them attractive targets for the synthesis of new materials with diverse potential applications. − In the last two decades, this class of materials has received significant interest among the scientific communities in the field of chemistry, engineering, physics, biology, and medicine. − Although the vast majority of the rapidly growing literature on MOFs focuses on the ordered structure, even the most carefully synthesized MOFs will contain a variety of defects. − In this context, defect tuning or defect engineering in MOFs is very promising as it offers additional opportunities to tune the porosity of MOFs locally, creates open metal sites, and modulates the surface properties.…”

Section: Introductionmentioning

confidence: 99%

White Light Emission Properties of Defect Engineered Metal–Organic Frameworks by Encapsulation of Eu³⁺ and Tb³⁺

Jena

Kaczmarek

Krishnaraj

et al. 2019

Crystal Growth & Design

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Defect engineering of metal–organic frameworks (MOFs) has already found applications in gas adsorption, storage, and heterogeneous catalysis. However, the role of defects in determining electrical, optical, and mechanical properties of MOFs is yet to be explored. Herein, we demonstrate the white light emission properties of two defect engineered MOFs (UiO-66 and MIL-53(Al)) through the encapsulation of lanthanide ions (Eu3+ and Tb3+). The defect sites are created by the use of a modulator (4-acetyl benzoic acid; AB) during the synthesis of MOFs. The color of the lanthanide functionalized UiO-66 could be tuned from white (UiO-66-AB) to green (Tb@UiO-66-AB), pale pink (Eu@UiO-66-AB), and yellowish-white (Tb/Eu@UiO-66-AB) when placed under a laboratory ultraviolet lamp (365 nm). Under the same conditions, the lanthanide functionalized MIL-53(Al) showed color changes from blue (MIL-53(Al)-AB) to cyan (Tb@MIL-53(Al)-AB), pink (Eu@MIL-53(Al)-AB), and white (Tb/Eu@MIL-53(Al)-AB). The luminescence properties of all the lanthanide encapsulated modulated MOFs have been well studied. Notably, by varying the excitation wavelength, a close to white light was obtained for the Tb/Eu@UiO-66-AB material (λex = 340 nm; CIE coordinates (x = 0.3290, y = 0.3934)) and Tb/Eu@MIL-53(Al)-AB (λex = 320 nm; CIE coordinates (x = 0.3204, y = 0.3873)). These observations indicate that lanthanide encapsulation at defect sites of MOFs allows more room for design and color tuning. The high thermal stabilities, good crystallinities, and tunable luminescence properties of MOFs reveal that these materials may have potential applications in white light emitting devices.

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Encapsulated Metallic Nanoparticles in Metal–Organic Frameworks: Toward Their Use in Catalysis

Cited by 2 publications

References 183 publications

Metal–Organic Frameworks as Catalysts for Organic Synthesis: A Critical Perspective

Metal–Organic Frameworks as Catalysts for Organic Synthesis: A Critical Perspective

White Light Emission Properties of Defect Engineered Metal–Organic Frameworks by Encapsulation of Eu³⁺ and Tb³⁺

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Encapsulated Metallic Nanoparticles in Metal–Organic Frameworks: Toward Their Use in Catalysis

Cited by 2 publications

References 183 publications

Metal–Organic Frameworks as Catalysts for Organic Synthesis: A Critical Perspective

Metal–Organic Frameworks as Catalysts for Organic Synthesis: A Critical Perspective

White Light Emission Properties of Defect Engineered Metal–Organic Frameworks by Encapsulation of Eu3+ and Tb3+

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White Light Emission Properties of Defect Engineered Metal–Organic Frameworks by Encapsulation of Eu³⁺ and Tb³⁺