From Transition Metals to Lanthanides to Actinides: Metal-Mediated Tuning of Electronic Properties of Isostructural Metal–Organic Frameworks

İslamoğlu, Timur; Ray, Debmalya; Li, Peng; Majewski, Marek B.; Akpınar, Işıl; Zhang, Xuan; Cramer, Christopher J.; Gagliardi, Laura; Farha, Omar K.

doi:10.1021/acs.inorgchem.8b01748

Cited by 86 publications

(127 citation statements)

References 63 publications

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“…on forces). Optimized structures and representative input files for the calculations are available online at https://github.com/fxcoudert/citable-data RESULTS AND DISCUSSION Ambient pressure PXRD patterns for each MOF are in good agreement with the simulated powder patterns (Figure S1) from reported crystal structures, [27][28] indicating that the UiO-66 structure is retained when synthesized with different metals. Nitrogen physisorption isotherms ( Figure S2) indicate that porosity of the UiO-66 MOFs is also maintained.…”

Section: Experimental Methodsmentioning

confidence: 52%

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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Section: Experimental Methodsmentioning

confidence: 52%

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

et al. 2020

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“…MOF‐based materials have been found to be suitable catalysts to produce certain products with high industrial value due to their functional active sites along with the potential inner porosity that allows guest molecules to access the pores [35, 36, 37] . MOFs show high versatility thanks to the ability of modifying the organic linker and metal node, which offers a fine‐tune control of the pore size or their inherent Lewis acidity, allowing the design of more selective processes [38–42] …”

Section: Introductionmentioning

confidence: 99%

Zr‐MOF‐808 as Catalyst for Amide Esterification

Villoria‐del‐Álamo

Rojas‐Buzo

García‐García

et al. 2020

Chemistry A European J

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“…Interestingly, most of the acceleration is associated with the facility with which water is displaced in the Ce case compared to Zr, reflecting the weaker bonding of water to the Ce node that has been documented experimentally. 74 Overall, our calculations show Ce IV -MOF-808 to be the fastest of all studied MOFs for the hydrolysis of sarin. We note that functionalization of the linkers of Ce IV -MOFs with, for example, -NH2 functional groups (that have been shown to enhance reactivity for their Zr IV analogues 7,22,24,26,28 ) and recently iodine groups 75 could offer additional opportunity to further enhance the reactivity of these systems.…”

Section: Reactivity Of Ce IV Vs Zr Iv Single-node Mofs In Sarin Hydromentioning

confidence: 61%

Computational Screening of Roles of Defects and Metal Substitution on Reactivity of Different Single- vs Double-Node Metal–Organic Frameworks for Sarin Decomposition

MomeniTaheri¹,

Cramer²

2019

Preprint

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Understanding how different factors affect the electronic prop-erties of metal-organic frameworks (MOFs) is critical to under-standing their potential for catalysis and to serve as catalyst supports. In this work, periodic dispersion corrected PBE cal-culations are performed to assess the catalytic activity of dif-ferent Zr6 vs Zr12 metal-organic frameworks (MOFs) for the heterogeneous catalytic hydrolysis of the chemical warfare agent (CWA) sarin. Using a comprehensive series of extended periodic models capable of capturing long-range sar-in/water/framework interactions in both Zr6 and Zr12 MOFs, the effect of numbers and morphologies of defective sites as well as ZrIV substitution with heavier CeIV are thoroughly in-vestigated. Our calculations show that hydrogen bonds in-volving both metal-oxide nodes and organic linkers can play important roles in the catalysis. Insights derived from this work should inform the design and realization of more effec-tive and robust next-generation MOF-based heterogeneous catalysts.

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From Transition Metals to Lanthanides to Actinides: Metal-Mediated Tuning of Electronic Properties of Isostructural Metal–Organic Frameworks

Cited by 86 publications

References 63 publications

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

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

Zr‐MOF‐808 as Catalyst for Amide Esterification

Computational Screening of Roles of Defects and Metal Substitution on Reactivity of Different Single- vs Double-Node Metal–Organic Frameworks for Sarin Decomposition

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