scholarly journals Preparation of Ruthenium Olefin Metathesis Catalysts Immobilized on MOF, SBA-15, and 13X for Probing Heterogeneous Boomerang Effect

Catalysts ◽  
2020 ◽  
Vol 10 (4) ◽  
pp. 438 ◽  
Author(s):  
Artur Chołuj ◽  
Wojciech Nogaś ◽  
Michał Patrzałek ◽  
Paweł Krzesiński ◽  
Michał J. Chmielewski ◽  
...  

Promoted by homogeneous Ru-benzylidene complexes, the olefin metathesis reaction is a powerful methodology for C-C double bonds formation that can find a number of applications in green chemical production. A set of heterogeneous olefin metathesis pre-catalysts composed of ammonium-tagged Ru-benzylidene complexes 4 (commercial FixCat™ catalyst) and 6 (in-house made) immobilized on solid supports such as 13X zeolite, metal-organic framework (MOF), and SBA-15 silica were obtained and tested in catalysis. These hybrid materials were doped with various amounts of ammonium-tagged styrene derivative 5—a precursor of a spare benzylidene ligand—in order to enhance pre-catalyst regeneration via the so-called release-return “boomerang effect”. Although this effect was for the first time observed inside the solid support, we discovered that non-doped systems gave better results in terms of the resulting turnover number (TON) values, and the most productive were hybrid catalysts composed of 4@MOF, 4@SBA-15, and 6@SBA-15.

Catalysts ◽  
2020 ◽  
Vol 10 (6) ◽  
pp. 687
Author(s):  
Gerard Pareras ◽  
Davide Tiana ◽  
Albert Poater

In the present work, a catalyst variation of the second-generation Hoveyda–Grubbs catalyst, particularly the ammonium-tagged Ru-alkylidene metathesis catalyst AquaMetTM, is under study, not simply to increase the efficiency in olefin metathesis but also the solubility in polar solvents. Moreover, this ionic catalyst was combined with the metal organic framework (MOF) (Cr)MIL-101-SO3−(Na·15-crown-5)+. We started from the experimental results by Grela et al., who increased the performance when the ruthenium catalyst was confined inside the cavities of the MOF, achieving non-covalent interactions between both moieties. Here, using density functional theory (DFT) calculations, the role of the ammonium N-heterocyclic carbene (NHC) tagged and the confinement effects are checked. The kinetics are used to compare reaction profiles, whereas SambVca steric maps and NCI plots are used to characterize the role of the MOF structurally and electronically.


2019 ◽  
Author(s):  
Timothée Stassin ◽  
Ivo Stassen ◽  
Joao Marreiros ◽  
Alexander John Cruz ◽  
Rhea Verbeke ◽  
...  

A simple solvent- and catalyst-free method is presented for the synthesis of the mesoporous metal-organic framework (MOF) MAF-6 (RHO-Zn(eIm)2) based on the reaction of ZnO with 2-ethylimidazole vapor at temperatures ≤ 100 °C. By translating this method to a chemical vapor deposition (CVD) protocol, mesoporous crystalline films could be deposited for the first time entirely from the vapor phase. A combination of PALS and Kr physisorption measurements confirmed the porosity of these MOF-CVD films and the size of the MAF-6 supercages (diam. ~2 nm), in close agreement with powder data and calculations. MAF-6 powders and films were further characterized by XRD, TGA, SEM, FTIR, PDF and EXAFS. The exceptional uptake capacity of the mesoporous MAF-6 in comparison to the microporous ZIF-8 is demonstrated by vapor-phase loading of a molecule larger than the ZIF-8 windows.


2018 ◽  
Vol 9 ◽  
pp. 2960-2967 ◽  
Author(s):  
Jan Hynek ◽  
Sebastian Jurík ◽  
Martina Koncošová ◽  
Jaroslav Zelenka ◽  
Ivana Křížová ◽  
...  

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.


2019 ◽  
Vol 10 (18) ◽  
pp. 2263-2272 ◽  
Author(s):  
Huaizhi Liu ◽  
Hao Peng ◽  
Yumeng Xin ◽  
Jiuyang Zhang

We reported for the first time using metal–organic framework (MOF) nanoparticles as effective nanofillers to significantly enhance the mechanical performance of hydrogels. The MOF hydrogels have been developed for drug delivery materials with high loading capacity and much extended drug releasing profiles.


2019 ◽  
Vol 6 (7) ◽  
pp. 1433-1437 ◽  
Author(s):  
Ziming Wang ◽  
Xingtao Xu ◽  
Jeonghun Kim ◽  
Victor Malgras ◽  
Ran Mo ◽  
...  

Metal–organic framework/polypyrrole hybrids are synthesized and directly used in capacitive deionization for the first time.


2018 ◽  
Vol 9 (12) ◽  
pp. 3152-3158 ◽  
Author(s):  
Caiyun Xu ◽  
Hang Liu ◽  
Dandan Li ◽  
Ji-Hu Su ◽  
Hai-Long Jiang

For the first time, the photoexcited charge separation in a metal–organic framework has been evidenced with clear ESR signals, based on efficient and selective photocatalytic oxidative coupling of amines.


Polymers ◽  
2019 ◽  
Vol 11 (12) ◽  
pp. 2015 ◽  
Author(s):  
Feng Zhang ◽  
Shuyi Chen ◽  
Shengqiang Nie ◽  
Jun Luo ◽  
Shaomin Lin ◽  
...  

In this study, a lanthanide metal organic framework based on the ligand of terephthalic acid derived from waste polyethylene terephthalate (PET) bottles was designed and synthesized. The structure and morphology of the Tb-BDC was investigated by X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM). The Tb-BDC displays a high selectivity and sensitivity towards picric acid (TNP). The luminescence intensities exhibit a linear relation, with a concentration of TNP over the range of 1 × 10−5–1 × 10−4 M, with a limit of detection of 1 × 10−5 M. The sensing mechanism is also discussed. This is the first time that waste PET materials have been used as the starting precursor of terephthalic acid (BDC) for the fabrication of lanthanide MOF (metal organic framework), which is applied in sensing TNP.


The Analyst ◽  
2019 ◽  
Vol 144 (16) ◽  
pp. 4887-4896 ◽  
Author(s):  
Mariyemu Tuergong ◽  
Patima Nizamidin ◽  
Abliz Yimit ◽  
Rena Simayi

The optical gas adsorption behaviors of [Zn2(bdc)2(dpNDI)]n membranes were studied for the first time. Under UV light irradiation, they exhibited a greater adsorption response to xylene gas with adsorption capacity of 6.46 μg cm−2 per unit surface.


2020 ◽  
Vol 56 (39) ◽  
pp. 5231-5234
Author(s):  
Arun Kumar Shukla ◽  
Javed Alam ◽  
Fekri Abdulraqeb Ahmed Ali ◽  
Mansour Alhoshan

In this study, for the first time, a highly permeable composite membrane was constructed by incorporating a zinc-based metal–organic framework (Zn-MOF) in a polyphenylsulfone matrix for the elevation of antifouling properties.


2015 ◽  
Vol 51 (36) ◽  
pp. 7637-7640 ◽  
Author(s):  
Dariusz Matoga ◽  
Marcin Oszajca ◽  
Marcin Molenda

A high proton-conducting metal–organic framework (PCMOF) is prepared for the first time by economical and environmentally-friendly mechanochemistry.


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