Enhanced Framework Rigidity of a Zeolitic Metal-Azolate via Ligand Substitution

Gao, Hongqiang; Wei, Wenjuan; Dong, Liyuan; Jiang, Xingxing; Wu, Rong; Lin, Zheshuai; Li, Wei

doi:10.3390/cryst7040099

Cited by 12 publications

(8 citation statements)

References 41 publications

(49 reference statements)

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“…Both structures contain tetrahedral coordinated Zn 2+ , with coordination arising from N atoms in the 2 and 4 positions. The additional N atom in the mtz ligand remains noncoordinating, and the cubic sodalite topology is adopted in each case . Values for E max and E min , alongside G max and G min , were calculated (and the former confirmed by nanoindentation measurements) to be ≈20% and 3% higher for the triazolate based structure.…”

Section: Theoretical Calculationsmentioning

confidence: 91%

Mechanical Properties in Metal–Organic Frameworks: Emerging Opportunities and Challenges for Device Functionality and Technological Applications

et al. 2017

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Some of the most remarkable recent developments in metal-organic framework (MOF) performance properties can only be rationalized by the mechanical properties endowed by their hybrid inorganic-organic nanoporous structures. While these characteristics create intriguing application prospects, the same attributes also present challenges that will need to be overcome to enable the integration of MOFs with technologies where these promising traits can be exploited. In this review, emerging opportunities and challenges are identified for MOF-enabled device functionality and technological applications that arise from their fascinating mechanical properties. This is discussed not only in the context of their more well-studied gas storage and separation applications, but also for instances where MOFs serve as components of functional nanodevices. Recent advances in understanding MOF mechanical structure-property relationships due to attributes such as defects and interpenetration are highlighted, and open questions related to state-of-the-art computational approaches for quantifying their mechanical properties are critically discussed.

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Section: Theoretical Calculationsmentioning

confidence: 91%

Mechanical Properties in Metal–Organic Frameworks: Emerging Opportunities and Challenges for Device Functionality and Technological Applications

et al. 2017

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“…20 Given the breadth of knowledge regarding this framework, UiO-66 is a well-established platform for investigating the mechanism of structural changes at high pressures. While numerous reports support the notion that changes to the organic linker [21][22] and topology [23][24] can impact the compressibility of MOFs, systematic studies into the effect of changes to the metal node are less prevalent. 25 Herein, we investigate the role of the metal-carboxylate bond in the compression of UiO-66 by varying the identity of the metal node from Zr-UiO-66 to Hf-UiO-66 and Ce-UiO-66.…”

Section: Introductionmentioning

confidence: 99%

“…Given the breadth of knowledge regarding this framework, UiO-66 is a well-established platform for investigating the mechanism of structural changes at high pressures. While numerous reports support the notion that changes to the organic linker − and topology , can impact the compressibility of MOFs, systematic studies into the effect of changes to the metal node are less prevalent. − UiO-66 provides an excellent platform to investigate these trends, as it is a robust framework that is known to retain its crystallinity at pressures greater than 1 GPa …”

Section: Introductionmentioning

confidence: 99%

Isolating the Role of the Node-Linker Bond in the Compression of UiO-66 Metal–Organic Frameworks

et al. 2020

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Understanding the mechanical properties of metal-organic frameworks (MOFs) is essential to the fundamental advancement and practical implementations of porous materials. Recent computational and experimental efforts have revealed correlations between mechanical properties and pore size, topology, and defect density. These results demonstrate the important role of the organic linker in the response of these materials to physical stresses. However, the impact of the coordination bond between the inorganic node and organic linker on the mechanical stability of MOFs has not been thoroughly studied. Here, we isolate the role of this node-linker coordination bond to systematically study the effect it plays in the compression of a series of isostructural MOFs, M-UiO-66 (M = Zr, Hf, or Ce). The bulk modulus (i.e. the resistance to compression under hydrostatic pressure) of each MOF is determined by in situ diamond anvil cell (DAC) powder X-ray diffraction measurements and density functional theory (DFT) simulations. These experiments reveal distinctive behavior of Ce-UiO-66 in response to pressures under one GPa. In situ DAC Raman spectroscopy and DFT calculations support the observed differences in compressibility between Zr-UiO-66 and the Ceanalogue. Monitoring changes in bond lengths as a function of pressure through DFT simulations provides a clear picture of those which shorten more drastically under pressure and those which resist compression. This study demonstrates that changes to the node-linker bond can have significant ramifications on the mechanical properties of MOFs. File list (2) download file view on ChemRxiv Isolating the Role of the Node-Linker Bond in the Compr... (830.80 KiB) download file view on ChemRxiv Electronic supporting information.pdf (1.12 MiB)

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“…First we, replaced the Im ligand in the structure with 1,2,4‐triazole. This system has been experimentally synthesized and reported as MAF‐7 . This amorphous model is referred to as a‐Zn‐MAF‐7 (Figure B).…”

Section: Introductionmentioning

confidence: 99%

Structural, electronic, and dielectric properties of a large random network model of amorphous zeolitic imidazolate frameworks and its analogues

Wang

et al. 2019

J Am Ceram Soc

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The amorphous zeolitic imidazolate frameworks (a-ZIFs) models and its analogues (with 918 or 810 atoms, respectively) are constructed based on a larger continuous random network (CRN) model of amorphous SiO 2 (a-SiO 2 ) model.The atomic, electronic, and dielectric properties of these structures, which possess different metal nodes and organic linkers, are investigated by well-defined density functional theory (DFT) calculations. The results suggest that all a-ZIFs have ultra-low dielectric constants and a large energy loss function (ELF), which suggests that they may be good candidates for electromagnetic absorptive materials.Most important, these a-ZIFs models offer a base-line model for other amorphous ZIFs for further research on models containing vacancies, defects, doping or under high pressure or high temperature. K E Y W O R D Samorphous, density functional theory, dielectric properties, electronic properties, zeolitic imidazolate frameworks

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Enhanced Framework Rigidity of a Zeolitic Metal-Azolate via Ligand Substitution

Cited by 12 publications

References 41 publications

Mechanical Properties in Metal–Organic Frameworks: Emerging Opportunities and Challenges for Device Functionality and Technological Applications

Mechanical Properties in Metal–Organic Frameworks: Emerging Opportunities and Challenges for Device Functionality and Technological Applications

Isolating the Role of the Node-Linker Bond in the Compression of UiO-66 Metal–Organic Frameworks

Structural, electronic, and dielectric properties of a large random network model of amorphous zeolitic imidazolate frameworks and its analogues

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