MOFs as multifunctional catalysts: One-pot synthesis of menthol from citronellal over a bifunctional MIL-101 catalyst

Cirujano, Francisco G.; Xamena, Françesc X. Llabrés i; Corma, Avelino

doi:10.1039/c2dt12480g

Cited by 136 publications

(75 citation statements)

References 32 publications

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“…This high variability, along with the possibility to introduce new functionalities in a pre-formed MOF by post-synthesis modification [10][11][12], allow to finely tune the chemical compositions, chemical environment and pore structures of the materials and thus, their reactivity. The Lewis acid catalytic properties of MOFs have already been demonstrated for many reactions, including cyanosilylation of carbonyl compounds [13][14][15][16], epoxide methanolysis [17], isomerizations of -pinene oxide and citronellal [18,19], Friedländer condensation [20], alkene cyclopropanation [21], etc. In many cases, the Lewis acid character of the MOF is induced by the creation of a coordination vacancy upon thermal removal of a solvent molecule (H 2 O) initially bound to the metallic nodes.…”

Section: Methodsmentioning

confidence: 99%

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: Methodsmentioning

confidence: 99%

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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“…This high variability, along with the possibility to introduce new functionalities in a pre-formed MOF by post-synthesis modification (Wang and Cohen, 2009;Zhang et al, 2009), allow to finely tune the chemical compositions, chemical environment and pore structures of the materials and thus, their reactivity. The Lewis acid catalytic properties of MOFs have already been demonstrated for many reactions, including cyanosilylation of carbonyl compounds (Fujita et al, 1994;Henschel et al, 2008;Horike et al, 2008;Schlichte et al, 2004), epoxide methanolysis (Wee et al, 2012), isomerizations of α-pinene oxide and citronellal (Alaerts et al, 2006;Cirujano et al, 2012), Friedländer condensation (Pérez-Mayoral and Cejka, 2011), alkene cyclopropanation (Corma et al, 2010b), etc. In many cases, the Lewis acid character of the MOF comes from the creation of a coordination vacancy upon thermal removal of a solvent molecule (usually H 2 O) initially bound to the metallic nodes.…”

Section: Introductionmentioning

confidence: 99%

Conversion of levulinic acid into chemicals: Synthesis of biomass derived levulinate esters over Zr-containing MOFs

Cirujano

Corma

Xamena

2015

Chemical Engineering Science

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Zr-containing metal-organic frameworks (MOFs) formed by terephthalate and 2-aminoterephthalate ligands (UiO-66-NH 2 ) are active and stable catalysts for the acid catalyzed esterification of levulinic acid with EtOH, n-BuOH and long-chain biomass derived alcohols, with activities comparable (in some cases superior) to other solid acid catalysts previously reported. The effect of functional group substitution at the ligand benzene ring, alcohol chain length, particle size and contents of defects on the catalytic activity of the MOFs are studied in detail. In UiO-66-NH 2 , a dual acid-base activation mechanism is proposed, in which levulinic acid is activated on Zr sites and the alcohol at the amino groups of the ligand. Large variations of the catalytic activity from batch to batch suggest that the active sites are located at defect positions associated to ligand deficiency of the solid. Particle size seems to have a minor impact only in UiO-66-NH 2 , in which diffusion of levulinic acid is somehow hindered due to the amino groups present in the linkers.

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“…Thus we have demonstrated that Pd@MIL-101 combined hydrogenation properties of the encapsulated Pd NPs and Lewis acid character of the Cr 3+ metallic nodes into a bifunctional catalyst for the one-pot sequential transformation of citronellal to isopulegol (acid catalyzed isomerization) and isopulegol to menthol (hydrogenation of C=C bond). [17] Analogously, we also showed that combination of metal-acid properties of Pd@MIL-101 and Pt@MIL-101 allows performing multi-step tandem reactions based on reductive amination of carbonyl compounds for the preparation of secondary amines and N-containing heterocycles. [18] Alternatively, the chemical environment inside the pore system of the MOF, along with long-range interactions and confinement effects imposed by the framework, can modulate the catalytic properties of the encapsulated NPs, thus altering their activity and the (shape-, chemo-, enantio-or regio-) selectivity of the catalytic reaction.…”

Section: Introductionmentioning

confidence: 85%

Pd@UiO‐66‐Type MOFs Prepared by Chemical Vapor Infiltration as Shape‐Selective Hydrogenation Catalysts

et al. 2015

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Host‐guest inclusion properties of UiO‐66 and UiO‐67 metal‐organic frameworks have been studied using ferrocene (FeCp2) as probe molecule. According to variable‐temperature solid‐state 1H and 13C CP‐MAS‐NMR, two different environments exist for adsorbed FeCp2 inside UiO‐66 and UiO‐67, which have been assigned to octahedral and tetrahedral cavities. At room temperature, a rapid exchange between these two adsorption sites occurs in UiO‐67, while at –80 °C the intracrystalline traffic of FeCp2 through the triangular windows is largely hindered. In UiO‐66, FeCp2 diffusion is already impeded at room temperature, in agreement with the smaller pore windows. Palladium nanoparticles (Pd NPs) encapsulated inside UiO‐66 and UiO‐67 have been prepared by chemical vapor infiltration of (allyl)Pd(Cp) followed by UV light irradiation. Infiltration must be carried out at low temperature (–10 °C) to avoid uncontrolled decomposition of the organometallic precursor and formation of Pd NPs at the external surface of the MOF. The resulting Pd‐MOFs are shape selective catalysts, as shown for the hydrogenation of carbonyl compounds with different steric hindrance.

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MOFs as multifunctional catalysts: One-pot synthesis of menthol from citronellal over a bifunctional MIL-101 catalyst

Cited by 136 publications

References 32 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

Conversion of levulinic acid into chemicals: Synthesis of biomass derived levulinate esters over Zr-containing MOFs

Pd@UiO‐66‐Type MOFs Prepared by Chemical Vapor Infiltration as Shape‐Selective Hydrogenation Catalysts

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