Effects of linker substitution on catalytic properties of porous zirconium terephthalate UiO-66 in acetalization of benzaldehyde with methanol

Timofeeva, Maria N.; Panchenko, Valentina N.; Jun, Jong Won; Ḥasan, Zubair; Matrosova, M. M.; Jhung, Sung Hwa

doi:10.1016/j.apcata.2013.11.039

Cited by 104 publications

(80 citation statements)

References 44 publications

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“…23% of the amount adsorbed at 50ºC). Both results indicate that UiO-66 contains twice as much Lewis acid centers than UiO-66-NH 2 , and their acid strength is higher, in agreement with the conclusions drawn in previous studies [23,30,31]. < Insert Figure 1 near here> …”

Section: Acid Properties Of Uio-66 and Uio-66-nhsupporting

confidence: 80%

“…A similar reactivity trend was also observed for benzaldehyde acetalization [31]. However, this is not the reactivity trend that we have observed in the present study for C12 esterification over UiO-66 and UiO-66-NH 2 .…”

Section: Esterification Of Lauric Acid (C12) With Methanol or Ethanolmentioning

confidence: 28%

“…Furthermore, experimental evidences by TPD of CO 2 [23] and FTIR of adsorbed CDCl 3 [31] also revealed the presence of basic sites of medium strength in UiO-66-NH 2 , which are absent in UiO-66. In the present work, we have used FTIR spectroscopy of adsorbed cyclohexanone to evaluate comparatively the acid properties of the UiO-66 and UiO-66-NH 2 samples that will be later used in the catalytic studies.…”

Section: Acid Properties Of Uio-66 and Uio-66-nhmentioning

confidence: 99%

“…As commented above, the acid character of UiO-66 type materials has been indirectly established for several acid catalyzed reactions [23][24][25], as well as directly determined experimentally by means of CO adsorption FTIR and microcalorimetry [30], FTIR spectroscopy of adsorbed 5-nonanone [31], temperature programmed desorption (TPD) of NH 3 [23], and has been theoretically evaluated by DFT [25].…”

Section: Acid Properties Of Uio-66 and Uio-66-nhmentioning

confidence: 99%

“…In principle, one could expect differences in the acid character of the two materials as a consequence of the electronic effects introduced by the amino groups of the linkers. In this sense, the groups of Ahn [23], de Vos [24,25] and Timofeeva [31] have recently reported the comparative catalytic properties of isoreticular UiOs bearing various functional groups in the terephthalate linkers. According to these authors, the catalytic properties of the UiOs are highly dependent on the acid character of the materials, and this acidity can be modulated by the presence of functional groups in the MOF structure.…”

Section: Esterification Of Lauric Acid (C12) With Methanol or Ethanolmentioning

confidence: 99%

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Zirconium-containing metal organic frameworks as solid acid catalysts for the esterification of free fatty acids: Synthesis of biodiesel and other compounds of interest

2015

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Zr-containing metal-organic frameworks (MOFs) formed by terephthalate (UiO-66) and 2-aminoterephthalate ligands (UiO-66-NH 2 ) are active and stable catalysts for the acid catalyzed esterification of various saturated and unsaturated fatty acids with MeOH and EtOH, with activities comparable (in some cases superior) to other solid acid catalysts previously reported in literature. Besides the formation of the corresponding fatty acid alkyl esters as biodiesel compounds (FAMEs and FAEEs), esterification of biomassderived fatty acids with other alcohols catalyzed by the Zr-MOFs allows preparing other compounds of interest, such as oleyl oleate or isopropyl palmitate, with good yields under mild conditions. 2

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Section: Acid Properties Of Uio-66 and Uio-66-nhsupporting

confidence: 80%

Section: Esterification Of Lauric Acid (C12) With Methanol or Ethanolmentioning

confidence: 28%

Section: Acid Properties Of Uio-66 and Uio-66-nhmentioning

confidence: 99%

Section: Acid Properties Of Uio-66 and Uio-66-nhmentioning

confidence: 99%

Section: Esterification Of Lauric Acid (C12) With Methanol or Ethanolmentioning

confidence: 99%

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Zirconium-containing metal organic frameworks as solid acid catalysts for the esterification of free fatty acids: Synthesis of biodiesel and other compounds of interest

2015

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Highly Stable and End‐group Tuneable Metal–Organic Framework/Polymer Composite for Superior Triboelectric Nanogenerator Application

Saurabh

Mollick

et al. 2022

Adv Materials Inter

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generations. This has necessitated the enhanced use of renewable forms of energy. While solar energy and wind energy are perhaps the most explored forms of renewables, other forms such as mechanical energy have received relatively less attention. In fact, the energy from diverse mechanical motions such as body motion, wind, and water tidal energy has been mostly squandered and ignored in the past. Fortunately, the scientific community has begun to take notice of the availability of such other energy sources available to us as a partial solution to the growing energy-related problems. [1,2] Indeed, in the recent decade, mechanical energy conversion technologies have witnessed substantial progress, especially in the area of distributed micro/nano-power sources, portable high-voltage sources, wearable electronics, and high-precision sensors. At the heart of this progress are the devices known as triboelectric nanogenerators (TENGs) which basically exploit the concept of charge separation accomplished by relative motion between two dissimilar materials in proximity, the well-known phenomenon of friction being an expression of the process. [3] The dissimilarity of materials emanates from Triboelectric nanogenerators (TENGs) are receiving significant attention lately as efficient mechanical energy harvesting devices. They are finding multiple uses in numerous low-power applications. Current TENG designs, although innovative, fall short on practical demands like performance tunability, modulatory, and stability. This invites further research in the use of new materials for TENGs. Metal-organic frameworks (MOFs) offer a unique feature of molecular tunability to optimize energy conversion which has been exploited in this study. Prototypal hybridization strategy is deployed on underexplored isoreticular subfamily UiO-66(Zr) MOFs through UiO-66-X/PVDF (X = H or Br) composites for TENG output tuning and amplification. UiO-66-X/PVDF exhibits good aquatic and thermal stability accompanying substantial boost in TENG power. Functionalized H 2 BDC linker improved surface roughness and potential. UiO-66-Br encased in PVDF matrix boosted charge and TENG performance by enhancing electrification. Computational details support observations. Device captures waste energy in a vertical contact-separation mode and functions consistently amidst diverse environmental settings. Functionalized TENG-2 delivers a V p-p of 110.41 V, which is 2.92 times and 14.12 times higher than unfunctionalized TENG-1 and PVDF film, respectively. Findings reveal maiden example of ligand-mediated functional group-driven performance tuning of TENG and mechanistic insight using isoreticular MOFs/PVDF composites.

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Zirconium‐oxo Nodes of MOFs with Tunable Electronic Properties Provide Effective ⋅OH Species for Enhanced Methane Hydroxylation

Fang

Tian

et al. 2022

Angewandte Chemie

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Direct conversion of methane to high valueadded oxygenates under mild conditions has attracted extensive interest. However, the over-oxidation of target products is usually unavoidable due to the easily excessive activation of CÀ H bond on the sites of supported metal species. Here, we identified the most efficient Zr-oxo nodes of UiO-66 metal-organic frameworks (MOFs) catalysts for the selective oxidation of methane with H 2 O 2 . These nodes were modified by three types of benzene 1, 4-dicarboxylates (NH 2 -BDC, H 2 BDC, and NO 2 -BDC). Detailed characterizations and DFT calculations revealed that these ligands can effectively tune the electronic properties of Zr-oxo nodes and the H 2 BDC ligand led to optimal electronic density of Zr-oxo nodes in UiO-66. Thus the UiO-66-H catalyst promoted the formation of * OH species that adsorbed on Zr-oxo nodes, and facilitated the activation of methane with a lower energy barrier and subsequent conversion to hydroxylation oxygenates with 100 % selectivity.

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Effects of linker substitution on catalytic properties of porous zirconium terephthalate UiO-66 in acetalization of benzaldehyde with methanol

Cited by 104 publications

References 44 publications

Zirconium-containing metal organic frameworks as solid acid catalysts for the esterification of free fatty acids: Synthesis of biodiesel and other compounds of interest

Zirconium-containing metal organic frameworks as solid acid catalysts for the esterification of free fatty acids: Synthesis of biodiesel and other compounds of interest

Highly Stable and End‐group Tuneable Metal–Organic Framework/Polymer Composite for Superior Triboelectric Nanogenerator Application

Zirconium‐oxo Nodes of MOFs with Tunable Electronic Properties Provide Effective ⋅OH Species for Enhanced Methane Hydroxylation

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