Chemoselective reduction of α,β-unsaturated carbonyl compounds with UiO-66 materials

Plessers, Eva; Vos, Dirk De; Roeffaers, Maarten B. J.

doi:10.1016/j.jcat.2016.05.013

Cited by 65 publications

(45 citation statements)

References 47 publications

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“…These pairs occupy the place of a missing formate group. The disappearance of the band at 2745 cm −1 after treatment with methanol, as well as the decreased intensity at 3676 cm −1 , indicate the removal of the terminal OH group and the decreasing amount of μ 3 ‐OH . After treatment with methanol, the peaks at 2823 and 2930 cm −1 are consistent with the C−H stretching vibrations of methoxy groups derived from methanol .…”

Section: Resultsmentioning

confidence: 74%

“…To prove the interaction of methanol and 4‐methylguaiacol with the Zr CUS on the inorganic nodes of the MOF‐808, FTIR spectroscopy was performed on MOF‐808‐T2, MOF‐808‐S6, and 4‐methylguaiacol‐loaded MOF‐808‐S6 from methanol. In the FTIR spectrum (Figure a), the sharp band for the MOF‐808‐T2 sample at 3676 cm −1 indicates μ 3 ‐OH groups, whereas at 2745 cm −1 hydrogen‐bonded OH/OH 2 pairs can be seen . These pairs occupy the place of a missing formate group.…”

Section: Resultsmentioning

confidence: 98%

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Geminal Coordinatively Unsaturated Sites on MOF‐808 for the Selective Uptake of Phenolics from a Real Bio‐Oil Mixture

et al. 2019

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The capping formate anions of the metal–organic framework (MOF) zirconium benzene‐1,3,5‐tricarboxylate (MOF‐808) were removed by a solvent exchange procedure, resulting in a formate‐free MOF‐808 sample containing “geminal” defects consisting of six coordinatively unsaturated sites (CUSs) on each of the Zr6 nodes. Adsorption experiments with this material showed that the uptake of 4‐methylguaiacol from a bio‐oil mixture was proportional to the number of defects and amounted to one mole adsorbed per mole of zirconium. The selective uptake behavior of MOF‐808 towards phenolic compounds was further evident from competitive adsorption experiments between furfuryl alcohol and 4‐methylguaiacol as well as from the excellent (20 wt % for phenolic compounds and <7 wt % for other compounds) uptake performance for real bio‐oil mixtures containing a large concentration and diversity of molecules.

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Section: Resultsmentioning

confidence: 74%

Section: Resultsmentioning

confidence: 98%

Geminal Coordinatively Unsaturated Sites on MOF‐808 for the Selective Uptake of Phenolics from a Real Bio‐Oil Mixture

et al. 2019

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“…Plessers et al [154] successfully employed UiO-66 and its analoguesf or chemoselective reduction of a,b-unsaturatedc arbonyl compounds. Plessers et al [154] successfully employed UiO-66 and its analoguesf or chemoselective reduction of a,b-unsaturatedc arbonyl compounds.…”

Section: Zirconiummentioning

confidence: 99%

Engineering Metal–Organic Framework Catalysts for C−C and C−X Coupling Reactions: Advances in Reticular Approaches from 2014–2018

Kousik

Velmathi

2019

Chemistry A European J

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Metal-organic frameworks (MOFs) are ac lass of crystalline porousm aterials that have been activelyu sed for several industrial and synthetica pplications.M OFs are spatially and geometrically extrapolatedc oordination polymers with intriguing properties such as tunable porosity and dimensionality.Int erms of their catalytic efficiency,MOFs combine the easy recoverability of heterogeneous catalysts with the increased selectivity of biological catalysts. It is therefore not surprising that alot of work on optimizing MOF catalysts for organic transformationsh as been carriedo ut over the past decade. In this review,recent developments in MOF catalysis are summarized, with special attention being paid to CÀC, CÀN, and CÀOc oupling reactions. The influence of pore size, pore environment, and load on catalytic activity is described. Post-synthetics tabilization techniques and hostguest interactions in caged MOF scaffolds are detailed. Mechanistic aspects pertaining to the use of MOFs in asymmetric heterogeneousc atalysis are highlighted and categorized.

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“…Furthermore, the energy‐dispersive X‐ray spectroscopy (EDS) mapping analysis of Pt void @MOF(Y) showed that the Zn, Ni, and Pt elements in Pt void @MOF(Y) are homogeneously distributed on the Echinoidea‐like structure (Figure E). Thus, the spatial distribution of incorporated Pt NPs in/on the MOF can be controlled by their addition sequence …”

Section: Methodsmentioning

confidence: 99%

Rational Localization of Metal Nanoparticles in Yolk–Shell MOFs for Enhancing Catalytic Performance in Selective Hydrogenation of Cinnamaldehyde

et al. 2019

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Supported metal nanoparticle (MNP) catalysts are of interest in heterogeneous catalysis because of their fascinating catalytic behavior,inresponse to challenges in the fine-chemicals industry. [1] However, the leaching/agglomeration of MNPs that usually occurs resultsi nadiminishment of their catalytic activity over time owing to the weak anchorage on supports. On the other hand, strong immobilization of supported stabilizers aroundM NPs could prohibit the catalytic activity of surface metal atoms. [2] Recently,e ncapsulating MNPs in porous materials such as zeolites, activated carbon,a nd metal-organic frameworks (MOFs) by means of appropriate anchorage has been regarded as as ustainable strategy to improve catalytic activity and facilitate catalyst recovery. [3] Moreover,t he porous structures can not only serve as templates for synthesizing monodisperse MNPs, but also provideawell-definedm icroenvironmentt hat can controlt he selectivity of catalytic reactions on the encapsulated MNPs and avoid the leaching of MNPs. [4] For example, Jiang and co-workersr eported Pt@MIL-125/Au as ah igh-performance photocatalystf or water splitting. [4h] Tang and co-workers synthesized sandwich MIL-101@Pt@MIL-101 for hydrogenation of a,b-unsaturated aldehydest ou nsaturated alcohols. [4i] Astruca nd co-workers preparedt ransition metal NPs/ ZIF-8 composites for H 2 generation on hydrolysis of ammoniaborane. [4j] To date, in porous-material-supported MNPs for heterogeneous catalysis, the MNPs either decorate the outer surfaceo r are completely incorporated within the porous materials. [5] In the former case, the MNPs immobilized on the outer surface have high surface energya nd tend to migrate and aggregate into larger particles;t his leads to loss of catalytic activity during continuous reactions. In addition, the weak metal-support interaction is also unfavorable for stability and selectivity. [6] In the latter case, the inner porouss pace can ensure uniform dispersion of incorporated MNPs with high stability and catalytic selectivity. [7] However, the criticalb ottleneck is the slow diffusion rate when the reactants pass through the long path in the support to access active sites of MNPs.T he slow diffusion would result in poor reactionefficiencyifthe rate-limiting step is diffusion of the reactant to the active sites or diffusion of product out of the catalyst. Clearly,t he spatial distribution of MNPs in the porousm aterials brings about at rade-off between the reaction efficiency and selectivity. [8] The selectiveh ydrogenationo fa,b-unsaturated aldehydes (C=Ov ersus C=C) to produce unsaturated alcohols is an essential step in the preparation of various fine chemicals, but achieving high selectivity to the unsaturated alcohols at high conversion is challenging. [9] The use of heterogeneousc atalysts is ap otential way to achieve both atom-efficient and environmentally friendly chemical procedures.I nt his work, cinnamaldehyde( CAL), as ar epresentative a,b-unsaturateda ldehyde, was chosen as am odel substrate...

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Chemoselective reduction of α,β-unsaturated carbonyl compounds with UiO-66 materials

Cited by 65 publications

References 47 publications

Geminal Coordinatively Unsaturated Sites on MOF‐808 for the Selective Uptake of Phenolics from a Real Bio‐Oil Mixture

Geminal Coordinatively Unsaturated Sites on MOF‐808 for the Selective Uptake of Phenolics from a Real Bio‐Oil Mixture

Engineering Metal–Organic Framework Catalysts for C−C and C−X Coupling Reactions: Advances in Reticular Approaches from 2014–2018

Rational Localization of Metal Nanoparticles in Yolk–Shell MOFs for Enhancing Catalytic Performance in Selective Hydrogenation of Cinnamaldehyde

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