Synthesis and Characterization of Amine-Functionalized Mixed-Ligand Metal–Organic Frameworks of UiO-66 Topology

Chavan, Sachin; Shearer, Greig C.; Svelle, Stian; Olsbye, Unni; Bonino, Francesca; Ethiraj, Jayashree; Lillerud, Karl Petter; Bordiga, Silvia

doi:10.1021/ic500607a

Cited by 168 publications

(148 citation statements)

References 40 publications

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“…The signal intensities of ABDC in UiO‐66‐Mix or ABPDC in UiO‐67‐Mix increased gradually with the increase of the feed ratio of H 2 ABDC/H 2 BDC or H 2 ABPDC/H 2 BPDC (Figure ), and the corresponding quantitative analysis is summarized in Table . Except for UiO‐67‐2, there was a slightly lower amount of amino groups in UiO‐66‐Mix and UiO‐67‐Mix than that in the feed (Table ), which was consistent with the reported results for other mixed‐linker MOFs . The structural integrity of UiO‐66‐Mix and UiO‐67‐Mix was confirmed by using powder X‐ray diffraction (PXRD; Figure S2).…”

Section: Resultssupporting

confidence: 87%

“…The difference between the FTIR spectra was hard to observe because of the similarities of the structures (Figures S1 and S3). To determine the molecular ratio of ABDC/BDC in UiO‐66‐Mix or ABPDC/BPDC in UiO‐67‐Mix, the mixed‐linker MOFs were digested in NaOH/D 2 O solution and analyzed by using 1 H NMR spectroscopy . The signal intensities of ABDC in UiO‐66‐Mix or ABPDC in UiO‐67‐Mix increased gradually with the increase of the feed ratio of H 2 ABDC/H 2 BDC or H 2 ABPDC/H 2 BPDC (Figure ), and the corresponding quantitative analysis is summarized in Table .…”

Section: Resultsmentioning

confidence: 99%

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Palladium(II)@Zirconium‐Based Mixed‐Linker Metal–Organic Frameworks as Highly Efficient and Recyclable Catalysts for Suzuki and Heck Cross‐Coupling Reactions

Sun

Liu

et al. 2016

ChemCatChem

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Two series of amine‐functionalized Zr‐based mixed‐linker metal–organic frameworks (MOFs; UiO‐66‐Mix and UiO‐67‐Mix) have been synthesized with different ratios of 1,4‐benzenedicarboxylate/2‐amino‐1,4‐benzenedicarboxylate and 4,4′‐biphenyldicarboxylic acid/2‐amino‐biphenyl‐4,4′‐dicarboxylic acid incorporated into their structures. The pendant amino groups were postmodified by the condensation reaction with pyridine‐2‐carboxaldehyde, and Pd metal centers were anchored onto the MOFs by coordination to the pyridylimine moieties. The two series of heterogeneous Pd catalysts (UiO‐66‐Mix‐PI‐Pd and UiO‐67‐Mix‐PI‐Pd) were utilized for the Suzuki and Heck cross‐coupling reactions in ethanol/water under mild reaction conditions and they showed a remarkably high catalytic activity. The porosity of the MOFs and the density of the metal binding sites of the Pd catalysts had great influence on the Suzuki and Heck cross‐coupling reactions. The best results were achieved with a very low Pd loading (0.054 mol %), and the use of UiO‐67‐3‐PI‐Pd catalyst led to the complete conversion of reaction substrates. Moreover, the catalysts were readily recovered and recycled in at least 10 cycles without significant leaching or loss of catalytic activity. The catalysts were generally applicable for different reaction substrates with various substituents in both Suzuki and Heck reactions.

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Section: Resultssupporting

confidence: 87%

Section: Resultsmentioning

confidence: 99%

Palladium(II)@Zirconium‐Based Mixed‐Linker Metal–Organic Frameworks as Highly Efficient and Recyclable Catalysts for Suzuki and Heck Cross‐Coupling Reactions

Sun

Liu

et al. 2016

ChemCatChem

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“…For Lewis acid catalyzed reactions it was shown that terephthalate defects are responsible for the catalytic activity of the UiO-66 material [23,24]. Moreover, functionalization of the 1,4-benzenedicarboxylate linker allows to obtain a family of isoreticular UiO-66 structures [23,[25][26][27][28]. Such modifications to some extent affect thermal and chemical stability, and also remarkably change the electronic properties of the active site.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic studies of aldol condensations in UiO-66 and UiO-66-NH 2 metal organic frameworks

Hajek

Vandichel

Voorde

et al. 2015

Journal of Catalysis

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Abstract:A full mechanistic investigation is proposed for the industrially important cross aldol condensation reaction of heptanal with benzaldehyde on the UiO-66 and the amino-functionalized UiO-66-NH 2 metal-organic frameworks to form jasminaldehyde. Several experimental studies indicate that the activity for the aldol condensation reaction can be increased by proper functionalization of the material, e.g. by introducing an additional basic amino site and thus creating a bifunctional acid-base catalyst for the aldol condensation. The precise molecular level origin for this behavior is to date unclear. Herein state-of-the-art Density-Functional Theory (DFT) calculations have been performed to unravel the mechanism of the cross and self aldol condensation of benzaldehyde and propanal. To this end free energy calculations have been performed both on extended cluster and periodic models. It is found that the mechanism on both catalysts is essentially the same, although a slightly stronger adsorption of the reactants and slightly lower barriers were found on the amino functionalized material, pointing towards higher initial activities. New experiments were performed to confirm these observations. It is indeed found that the initial activity towards cross aldol condensation on the amino functionalized material is higher, although after about 40 min of reaction both materials become equally active. Our results furthermore point out that the basic amino groups may promote side reactions such as imine formation, which is induced by water. The study as presented can assist to engineer materials at the molecular level towards the desired products.

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“…[4][5][6][7][8] In particular, the combination of two types of rigid ligands may enhance the energy-transfer efficiency from ligand to metal ion and improve the luminescent properties of MOFs due to the so-called "antenna effect". 9,10 Recently, the tetrazole-based ligands have attracted much attention, 11 (1).…”

mentioning

confidence: 99%

A novel 3D zinc metal–organic framework based on the tetrazole-containing ligand and tricarboxylic acid

Wang

Feng

Xie

et al. 2015

Inorganic Chemistry Communications

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Synthesis and Characterization of Amine-Functionalized Mixed-Ligand Metal–Organic Frameworks of UiO-66 Topology

Abstract: A series of amine functionalized mixed linkerMOFs of idealized structural formula

Cited by 168 publications

References 40 publications

Palladium(II)@Zirconium‐Based Mixed‐Linker Metal–Organic Frameworks as Highly Efficient and Recyclable Catalysts for Suzuki and Heck Cross‐Coupling Reactions

Palladium(II)@Zirconium‐Based Mixed‐Linker Metal–Organic Frameworks as Highly Efficient and Recyclable Catalysts for Suzuki and Heck Cross‐Coupling Reactions

Mechanistic studies of aldol condensations in UiO-66 and UiO-66-NH 2 metal organic frameworks

A novel 3D zinc metal–organic framework based on the tetrazole-containing ligand and tricarboxylic acid

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