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 ◽  
...  
2020 ◽  
Vol 10 (23) ◽  
pp. 8077-8085
Author(s):  
Werner R. Heinz ◽  
Raphael Junk ◽  
Iker Agirrezabal-Telleria ◽  
Bart Bueken ◽  
Hana Bunzen ◽  
...  

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


2019 ◽  
Vol 48 (32) ◽  
pp. 12031-12039 ◽  
Author(s):  
Werner R. Heinz ◽  
Tim Kratky ◽  
Markus Drees ◽  
Andreas Wimmer ◽  
Ondřej Tomanec ◽  
...  

Mixed precious-group metal–organic frameworks [RuxRh3−x(BTC)2] of the HKUST-1-type were synthesized and characterized (PXRD, BET, IR, Raman, XPS, TGA, SS-UV/VIS, EA, and HR-TEM).


2020 ◽  
Author(s):  
Adam Sapnik ◽  
Duncan Johnstone ◽  
Sean M. Collins ◽  
Giorgio Divitini ◽  
Alice Bumstead ◽  
...  

<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>


2020 ◽  
Author(s):  
Daniel Bůžek ◽  
Slavomír Adamec ◽  
Kamil Lang ◽  
Jan Demel

<div><p>UiO-66 is a zirconium-based metal-organic framework (MOF) that has numerous applications. Our group recently determined that UiO-66 is not as inert in aqueous dispersions as previously reported in the literature. The present work therefore assessed the behaviour of UiO-66 in buffers: 2-amino-2-(hydroxymethyl)-1,3-propanediol (TRIS), 4-(2-hydroxyethyl)piperazine-1-ethane sulfonic acid (HEPES), N-ethylmorpholine (NEM) and phosphate buffer (PB), all of which are commonly used in many UiO-66 applications. High pressure liquid chromatography and inductively coupled plasma mass spectrometry were used to monitor degradation of the MOF. In each buffer, the terephthalate linker was released to some extent, with a more pronounced leaching effect in the saline forms of these buffers. The HEPES buffer was found to be the most benign, whereas NEM and PB should be avoided at any concentration as they were shown to rapidly degrade the UiO-66 framework. Low concentration TRIS buffers are also recommended, although these offer minimal buffer capacity to adjust pH. Regardless of the buffer used, rapid terephthalate release was observed, indicating that the UiO-66 was attacked immediately after mixing with the buffer. In addition, the dissolution of zirconium, observed in some cases, intensified the UiO-66 decomposition process. These results demonstrate that sensitive analytical techniques have to be used to monitor the release of MOF components so as to quantify the stabilities of these materials in liquid environments.</p></div>


2021 ◽  
Author(s):  
Isabel Abánades Lázaro ◽  
Neyvis Almora-Barrios ◽  
Sergio Tatay ◽  
Catalin Popescu ◽  
Carlos Martí-Gastaldo

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...


2018 ◽  
Vol 140 (32) ◽  
pp. 10191-10197 ◽  
Author(s):  
Hana Bunzen ◽  
Felicitas Kolbe ◽  
Andreas Kalytta-Mewes ◽  
German Sastre ◽  
Eike Brunner ◽  
...  

2019 ◽  
Author(s):  
Marco Taddei ◽  
Giulia M. Schukraft ◽  
Michael E. A. Warwick ◽  
Davide Tiana ◽  
Matthew McPherson ◽  
...  

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.


2018 ◽  
Vol 140 (37) ◽  
pp. 11581-11584 ◽  
Author(s):  
Stefano Dissegna ◽  
Pia Vervoorts ◽  
Claire L. Hobday ◽  
Tina Düren ◽  
Dominik Daisenberger ◽  
...  

2020 ◽  
Vol 124 (7) ◽  
pp. 4065-4072 ◽  
Author(s):  
Gloria Capano ◽  
Francesco Ambrosio ◽  
Stavroula Kampouri ◽  
Kyriakos C. Stylianou ◽  
Alfredo Pasquarello ◽  
...  

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