Thermal defect engineering of precious group metal–organic frameworks: impact on the catalytic cyclopropanation reaction

2020 ◽  
Vol 10 (23) ◽  
pp. 8077-8085
Author(s):  
Werner R. Heinz ◽  
Raphael Junk ◽  
Iker Agirrezabal-Telleria ◽  
Bart Bueken ◽  
Hana Bunzen ◽  
...  
Keyword(s):  
Metal Organic Frameworks ◽  
Analytical Tool ◽  
Defect Engineering ◽  
Group Metal ◽  
Thermal Defect ◽  
Metal Organic

This work highlights the catalytic cyclopropanation and its characteristics as a novel analytical tool to investigate complex MOF structures.

Thermal Defect Engineering of Precious Group Metal–Organic Frameworks: A Case Study on Ru/Rh-HKUST-1 Analogues

2020 ◽  
Vol 12 (36) ◽  
pp. 40635-40647 ◽  
Author(s):  
Werner R. Heinz ◽  
Iker Agirrezabal-Telleria ◽  
Raphael Junk ◽  
Jan Berger ◽  
Junjun Wang ◽  
...  
Keyword(s):  
Metal Organic Frameworks ◽  
Defect Engineering ◽  
Group Metal ◽  
Thermal Defect ◽  
Metal Organic

Engineering Porosity Through Defects in a Giant Pore Metal–Organic Framework

2020 ◽  
Author(s):  
Adam Sapnik ◽  
Duncan Johnstone ◽  
Sean M. Collins ◽  
Giorgio Divitini ◽  
Alice Bumstead ◽  
...  
Keyword(s):  
Distribution Function ◽  
Ball Milling ◽  
Local Structure ◽  
Pair Distribution Function ◽  
Function Analysis ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
Defect Engineering ◽  
Metal Organic ◽  
Unsaturated Metal Sites

<p>Defect engineering is a powerful tool that can be used to tailor the properties of metal–organic frameworks (MOFs). Here, we incorporate defects through ball milling to systematically vary the porosity of the giant pore MOF, MIL-100 (Fe). We show that milling leads to the breaking of metal–linker bonds, generating more coordinatively unsaturated metal sites, and ultimately causes amorphisation. Pair distribution function analysis shows the hierarchical local structure is partially</p><p>retained, even in the amorphised material. We find that the solvent toluene stabilises the MIL-100 (Fe) framework against collapse and leads to a substantial rentention of porosity over the non-stabilised material.</p>

scholarly journals Linker depletion for missing cluster defects in non-UiO Metal-Organic Frameworks

2021 ◽  
Author(s):  
Isabel Abánades Lázaro ◽  
Neyvis Almora-Barrios ◽  
Sergio Tatay ◽  
Catalin Popescu ◽  
Carlos Martí-Gastaldo
Keyword(s):  
Metal Organic Frameworks ◽  
Defect Chemistry ◽  
Defect Engineering ◽  
Preferential Formation ◽  
Metal Organic

Defect engineering is a valuable tool to tune the properties of Metal-Organic Frameworks. However, defect chemistry remains still predominantly limited to UiO-type MOFs. We describe the preferential formation of missing...

scholarly journals Band Gap Modulation in Zirconium-Based Metal-Organic Frameworks by Defect Engineering

2019 ◽  
Author(s):  
Marco Taddei ◽  
Giulia M. Schukraft ◽  
Michael E. A. Warwick ◽  
Davide Tiana ◽  
Matthew McPherson ◽  
...  
Keyword(s):  
Band Gap ◽  
Gas Phase ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
Benzoic Acids ◽  
Defect Engineering ◽  
Metal Organic ◽  
Band Gap Modulation ◽  
Valence Band Energy ◽  
Defective Sites

We report a defect-engineering approach to modulate the band gap of zirconium-based metal-organic framework UiO-66, enabled by grafting of a range of amino-functionalised benzoic acids at defective sites. Defect engineered MOFs were obtained by both post-synthetic exchange and modulated synthesis, featuring band gap in the 4.1-3.3 eV range. Ab-initio calculations suggest that shrinking of the band gap is mainly due to an upward shift of the valence band energy, as a result of the presence of light-absorbing monocarboxylates. The photocatalytic properties of defect-engineered MOFs towards CO<sub>2</sub> reduction to CO in the gas phase and degradation of Rhodamine B in water were tested, observing improved activity in both cases, in comparison to a defective UiO-66 bearing formic acid as the defect-compensating species.

scholarly journals Tuning the Mechanical Response of Metal–Organic Frameworks by Defect Engineering

2018 ◽  
Vol 140 (37) ◽  
pp. 11581-11584 ◽  
Author(s):  
Stefano Dissegna ◽  
Pia Vervoorts ◽  
Claire L. Hobday ◽  
Tina Düren ◽  
Dominik Daisenberger ◽  
...  
Keyword(s):  
Mechanical Response ◽  
Metal Organic Frameworks ◽  
Defect Engineering ◽  
Metal Organic

scholarly journals Defects in metal–organic frameworks: a compromise between adsorption and stability?

2016 ◽  
Vol 45 (10) ◽  
pp. 4352-4359 ◽  
Author(s):  
A. W. Thornton ◽  
R. Babarao ◽  
A. Jain ◽  
F. Trousselet ◽  
F.-X. Coudert
Keyword(s):  
Metal Organic Frameworks ◽  
Defect Engineering ◽  
Metal Organic

Defect engineering has arisen as a promising approach to tune and optimise the adsorptive performance of metal–organic frameworks.

scholarly journals Direct Imaging of Correlated Defect Nanodomains in a Metal-Organic Framework

2020 ◽  
Author(s):  
Duncan Johnstone ◽  
Francesca Firth ◽  
Clare P. Grey ◽  
Paul A. Midgley ◽  
Matthew Cliffe ◽  
...  
Keyword(s):  
Crystal Growth ◽  
Electron Diffraction ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
Synthetic Control ◽  
Defect Engineering ◽  
Nanoscale Characterization ◽  
Metal Organic ◽  
Image Defect ◽  
Scanning Electron

<p>Defect engineering can enhance key properties of metal-organic frameworks (MOFs). Tailoring the distribution of defects, for example in correlated nanodomains, requires characterization across length scales. However, a critical nanoscale characterization gap has emerged between the bulk diffraction techniques used to detect defect nanodomains and the sub-nanometre imaging used to observe individual defects. Here, we demonstrate that the emerging technique of scanning electron diffraction (SED) can bridge this gap. We directly image defect nanodomains in the MOF UiO-66(Hf) over an area of ca. 1 000 nm and with a spatial resolution ca. 5 nm to reveal domain morphology and distribution. Based on these observations, we suggest possible crystal growth processes underpinning synthetic control of defect nanodomains. We also identify likely dislocations and small angle grain boundaries, illustrating that SED could be a key technique in developing the potential for engineering the distribution of defects, or “microstructure”, in functional MOF design.</p>

scholarly journals Direct Imaging of Correlated Defect Nanodomains in a Metal-Organic Framework

2020 ◽  
Author(s):  
Duncan Johnstone ◽  
Francesca Firth ◽  
Clare P. Grey ◽  
Paul A. Midgley ◽  
Matthew Cliffe ◽  
...  
Keyword(s):  
Crystal Growth ◽  
Electron Diffraction ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
Synthetic Control ◽  
Defect Engineering ◽  
Nanoscale Characterization ◽  
Metal Organic ◽  
Image Defect ◽  
Scanning Electron

<p>Defect engineering can enhance key properties of metal-organic frameworks (MOFs). Tailoring the distribution of defects, for example in correlated nanodomains, requires characterization across length scales. However, a critical nanoscale characterization gap has emerged between the bulk diffraction techniques used to detect defect nanodomains and the sub-nanometre imaging used to observe individual defects. Here, we demonstrate that the emerging technique of scanning electron diffraction (SED) can bridge this gap. We directly image defect nanodomains in the MOF UiO-66(Hf) over an area of ca. 1 000 nm and with a spatial resolution ca. 5 nm to reveal domain morphology and distribution. Based on these observations, we suggest possible crystal growth processes underpinning synthetic control of defect nanodomains. We also identify likely dislocations and small angle grain boundaries, illustrating that SED could be a key technique in developing the potential for engineering the distribution of defects, or “microstructure”, in functional MOF design.</p>

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