scholarly journals Synthesis, structure and thermal stability of a mesoporous titanium(III) amine containing MOF with improved hydrogen sorption properties

Author(s):  
Timothy Steenhaut ◽  
Séraphin Lacour ◽  
Gabriella Barozzino-Consiglio ◽  
Koen Robeyns ◽  
Robin Crits ◽  
...  

The first mesoporous bimetallic TiIII/Al metal-organic framework (MOF) containing amine functionalities on its linkers has been selectively obtained by converting the cheap commercially available (TiCl3)3AlCl3 into Ti3-xAlxCl3(THF)3 and reacting this complex with 2-aminoterephthalic acid in DMF under soft solvothermal conditions. This compound is structurally related to the previously described NH2-MIL-101(M) (M = Cr, Al and Fe) MOFs. Thermal gravimetric analyses and in situ PXRD measurements demonstrated that this highly air-sensitive TiIII-containing MOF is structurally stable up to 200°C. Nuclear magnetic resonance (NMR) spectroscopy, elemental and inductively-coupled plasma (ICP) analyses revealed that NH2-MIL-101(TiIII) contains trinuclear Ti3(μ3-O)Cl(DMF)2(RCOO)6 clusters with strongly bound DMF molecules, and a small amount of aluminum. Sorption experiments reveal a higher affinity of this MOF for hydrogen compared to the previously described monometallic unfunctionalized MIL-101(TiIII) MOF.

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>


2010 ◽  
Vol 59 (4) ◽  
pp. 733-740 ◽  
Author(s):  
M. P. Yutkin ◽  
M. S. Zavakhina ◽  
D. G. Samsonenko ◽  
D. N. Dybtsev ◽  
V. P. Fedin

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>


2012 ◽  
Vol 14 (32) ◽  
pp. 11327 ◽  
Author(s):  
Liangliang Huang ◽  
Kaushik L. Joshi ◽  
Adri C. T. van Duin ◽  
Teresa J. Bandosz ◽  
Keith E. Gubbins

2021 ◽  
Vol 897 ◽  
pp. 57-62
Author(s):  
Omneya A. Koriem ◽  
Ahmed H. El-Shazly ◽  
Marwa F. El-Kady

UiO-66 is a zirconium-based metal organic framework (MOF). It was synthesized and used by researchers due to its high water, chemical and thermal stability. The mentioned reasons in addition to other excellent properties made them a highly competitive materials for a variety of industrial problems. This study investigates the effect of the reaction time on the characteristics of the prepared UiO-66 nanoparticles. UiO-66 was synthesized by the solvothermal method and the reaction was left to take place for 18, 21 and 24 hours. UiO-66 was characterized using X-ray Diffraction (XRD) and Fourier-Transform Infrared (FTIR), the results showed that it has the same patterns and functional groups of the previously reported UiO-66. In addition, Scanning Electron Microscopy (SEM) was used to confirm the morphology of UiO-66. The smallest particle size around 200 nm was obtained at 18 hours. To investigate the thermal stability of the prepared UiO-66, Thermogravimetry analysis (TGA) was conducted. The results matched well with the literature and confirm that UiO-66 is thermally stable up to 500°C.


2018 ◽  
Vol 2 (5) ◽  
pp. 942-951 ◽  
Author(s):  
Feroz Ahmad Sofi ◽  
Kowsar Majid

Ag/Ag3PO4 functionalised MIL-53(Fe) composite structures with superior visible light photocatalytic activity and thermal stability for the degradation of organic pollutants.


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