Immobilisation of a molecular epoxidation catalyst on UiO-66 and -67: the effect of pore size on catalyst activity and recycling

Kaposi, Marlene; Cokoja, Mirza; Hutterer, Christine H.; Hauser, Simone A.; Kaposi, Tobias; Klappenberger, Florian; Pöthig, Alexander; Barth, Johannes V.; Herrmann, Wolfgang A.; Kühn, Fritz E.

doi:10.1039/c5dt01340b

Cited by 46 publications

(40 citation statements)

References 55 publications

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“…These four solids were post-synthetically modified with salicylaldehyde to form a Schiff base-like ligand which later is used to anchor a molybdenum complex (Figure 7). [78] The activity of these catalysts was studied in the oxidation of olefins using TBHP as oxidant. The Mo content in UiO- catalyst indicates that the framework has remained intact during recycling.…”

Section: Uio-66-nh 2 In Catalysismentioning

confidence: 99%

Engineering UiO‐66 Metal Organic Framework for Heterogeneous Catalysis

et al. 2019

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frameworks (MOFs) are currently attracting considerable attention as heterogeneous catalysts at moderate temperatures, mainly for liquid-phase reactions. Since structural stability is one of the major concerns for the use of MOFs in catalysis, particularly considering that frequently some of the reported MOF materials are very unstable, the interest in this area has been focused on those MOFs exhibiting the highest structural robustness, UiO-66 being among the most widely used. Two introductory sections deal with the synthesis, structure and main properties of UiO-66, including its remarkable thermal (up to 350°C) and chemical (aqueous solution in a wide pH range) stability. The main body of the review summarizes those examples of using UiO-66 in catalysis grouped according to the nature of the active sites, starting with the use of UiO-66 as Lewis acids. In this section, emphasis has been made in the recent strategies to create structural defects in a controlled way that generate Lewis acidity. Other sections cover examples illustrating substituted terephthalate as active sites and the evidence that there is a synergy between acid and basic sites in close proximity that make some of these UiO-66 with substituents at the linker to act as dual acid-base catalysts. Other sections are focused on the use of UiO-66 as hosts of metal nanoparticles, metal oxides and other host, remarking the influence that the nature of UiO-66 and the possible presence of substituents in the framework play on the activity of the incorporated guest. The last section summarizes the current state of the art in the use of UiO-66 in catalysis and provides our views on future developments regarding the application of UiO-66 in industrial processes.

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Section: Uio-66-nh 2 In Catalysismentioning

confidence: 99%

Engineering UiO‐66 Metal Organic Framework for Heterogeneous Catalysis

et al. 2019

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“…The TGA traces of La‐PhBTTc and La‐ThBTB showed a first mass loss up to T =∼150 °C ( vide supra ), which is much lower than that for La‐BTTc (Figure ). This difference can be attributed to the different channel size of the PCPs, as larger channels facilitate the diffusion of solvents . The traces showed a clear plateau after the release of the solvent molecules, which is followed by a second mass loss associated with thermal decomposition.…”

Section: Resultsmentioning

confidence: 99%

Design and Synthesis of Porous Coordination Polymers with Expanded One‐Dimensional Channels and Strongly Lewis‐Acidic Sites

et al. 2017

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New porous coordination polymers (PCPs) consisting of La III cations and thiophene-based tritopic organic linkers, La-ThBTB and La-PhBTTc, are synthesized and structurally characterized. While these La-PCPs exhibit the same type of one-dimensional hexagonal channels, their thermal and chemical stability vary significantly with respect to each other, thus demonstrating the crucial importance of the design of the skeletal structure of the organic linker. Because of the large channel sizes and strong Lewis acidity of these La-PCPs, the catalytic activity in the Lewis-acidcatalyzed cyanosilylation of carbonyl compounds shows among the highest reported so far for PCPs.

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“…Considering the moderate BET surface area and pore volume of Titanium incorporated with NH 2 -UiO-66, it is likely that the high CO 2 capacity is due to the average pore diameter being of an optimal size to confine CO 2 molecules. 35 This suggests that Zr in the original NH 2 -UiO-66 has been substituted by Ti. The Ti-O ring sterically hinders access to the stronger adsorption sites at the metal cluster.…”

Section: Co 2 Adsorptionmentioning

confidence: 99%

Postsynthesis of Titanium Incorporated With Amino-Functionalization Uio-66 for Enhancing Co2 Uptake

Ge¹,

Wu²,

Wang³

et al. 2019

Quim. Nova

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Metal-organic frameworks (MOFs) are promising nanomaterials with unprecedented capacity to store small molecules. Titanium cooperated with NH 2-UiO-66 were prepared via post synthesis modifications approach and their structures and properties were characterized by X-raydiffraction,Fourier transform infrared spectroscopy, thermogravimetric analysis, nitrogen adsorption isotherms, and scanning electron microscopy. The resultant titanium cooperated with NH 2-UiO-66 showed excellent performance for CO 2 adsorption via the formation of oxo-bridged hetero-Zr-Ti clusters. This result clearly demonstrates that the smaller Ti ions exchanged with the Zr ions of NH 2-UiO-66 may decrease the pore sizes within the framework to be closer to the ideal pore sizes for CO 2 adsorption.

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Immobilisation of a molecular epoxidation catalyst on UiO-66 and -67: the effect of pore size on catalyst activity and recycling

Cited by 46 publications

References 55 publications

Engineering UiO‐66 Metal Organic Framework for Heterogeneous Catalysis

Engineering UiO‐66 Metal Organic Framework for Heterogeneous Catalysis

Design and Synthesis of Porous Coordination Polymers with Expanded One‐Dimensional Channels and Strongly Lewis‐Acidic Sites

Postsynthesis of Titanium Incorporated With Amino-Functionalization Uio-66 for Enhancing Co2 Uptake

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