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 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 Stepwise collapse of a giant pore metal–organic framework

2021 ◽  
Vol 50 (14) ◽  
pp. 5011-5022 ◽  
Author(s):  
Adam F. Sapnik ◽  
Duncan N. Johnstone ◽  
Sean M. Collins ◽  
Giorgio Divitini ◽  
Alice M. Bumstead ◽  
...  
Keyword(s):  
Distribution Function ◽  
Hierarchical Structure ◽  
Pair Distribution Function ◽  
Function Analysis ◽  
Metal Organic Framework ◽  
Defect Engineering ◽  
Structural Collapse ◽  
The Hierarchical Structure ◽  
Metal Organic ◽  
Organic Framework

Defect engineering is used to augment the porosity of MIL-100. Incorporation of defects leads to structural collapse and ultimately causes amorphisation. Pair distribution function analysis reveals a stepwise collapse of the hierarchical structure.

Ultrasound-driven preparation and pair distribution function-assisted structure solution of a copper-based layered coordination polymer

2014 ◽  
Vol 43 (27) ◽  
pp. 10438-10442 ◽  
Author(s):  
M. Infas Mohideen ◽  
Phoebe K. Allan ◽  
Karena W. Chapman ◽  
Joseph A. Hriljac ◽  
Russell E. Morris
Keyword(s):  
Distribution Function ◽  
Coordination Polymer ◽  
Polymer Material ◽  
Pair Distribution Function ◽  
Function Analysis ◽  
Metal Organic Framework ◽  
Ultrasound Treatment ◽  
Structure Solution ◽  
Metal Organic ◽  
Organic Framework

Pair distribution function analysis has been used to solve the structure of a coordination polymer material formed by ultrasound treatment of a metal–organic framework.

scholarly journals The nanoscaled metal-organic framework ICR-2 as a carrier of porphyrins for photodynamic therapy

2018 ◽  
Vol 9 ◽  
pp. 2960-2967 ◽  
Author(s):  
Jan Hynek ◽  
Sebastian Jurík ◽  
Martina Koncošová ◽  
Jaroslav Zelenka ◽  
Ivana Křížová ◽  
...  
Keyword(s):  
Inorganic Chemistry ◽  
Photodynamic Therapy ◽  
Photophysical Properties ◽  
Metal Organic Framework ◽  
Metal Organic Frameworks ◽  
Biological Applications ◽  
Nanoparticle Surface ◽  
Metal Organic ◽  
Unsaturated Metal Sites ◽  
First Time

Nanosized porphyrin-containing metal-organic frameworks (MOFs) attract considerable attention as solid-state photosensitizers for biological applications. In this study, we have for the first time synthesised and characterised phosphinate-based MOF nanoparticles, nanoICR-2 (Inorganic Chemistry Rez). We demonstrate that nanoICR-2 can be decorated with anionic 5,10,15,20-tetrakis(4-R-phosphinatophenyl)porphyrins (R = methyl, isopropyl, phenyl) by utilizing unsaturated metal sites on the nanoparticle surface. The use of these porphyrins allows for superior loading of the nanoparticles when compared with commonly used 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin. The nanoICR-2/porphyrin composites retain part of the free porphyrins photophysical properties, while the photodynamic efficacy is strongly affected by the R substituent at the porphyrin phosphinate groups. Thus, phosphinatophenylporphyrin with phenyl substituents has the strongest photodynamic efficacy due to the most efficient cellular uptake.

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 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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