Phosphine and phosphine oxide groups in metal–organic frameworks detected by P K-edge XAS

Morel, Flavien L.; Pin, Sonia; Huthwelker, Thomas; Ranocchiari, Marco; Bokhoven, Jeroen A. van

doi:10.1039/c4cp05151c

Cited by 25 publications

(14 citation statements)

References 33 publications

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“…Further evidence that no electronic interaction is responsible for the selectivity change was provided by preparing MOFs that feature strong coordinative bonds with Co such as phosphine MOFs (P-MOFs) 15,[36][37][38] . Such phosphine solid ligands can coordinate Co as supported by the literature 39 and by our DFT P-Co binding energies ( Supplementary Table 15 and Suplementary Fig.…”

Section: Resultsmentioning

confidence: 99%

Metal-organic frameworks as kinetic modulators for branched selectivity in hydroformylation

et al. 2020

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Finding heterogeneous catalysts that are superior to homogeneous ones for selective catalytic transformations is a major challenge in catalysis. Here, we show how micropores in metal-organic frameworks (MOFs) push homogeneous catalytic reactions into kinetic regimes inaccessible under standard conditions. Such property allows branched selectivity up to 90% in the Co-catalysed hydroformylation of olefins without directing groups, not achievable with existing catalysts. This finding has a big potential in the production of aldehydes for the fine chemical industry. Monte Carlo and density functional theory simulations combined with kinetic models show that the micropores of MOFs with UMCM-1 and MOF-74 topologies increase the olefins density beyond neat conditions while partially preventing the adsorption of syngas leading to high branched selectivity. The easy experimental protocol and the chemical and structural flexibility of MOFs will attract the interest of the fine chemical industries towards the design of heterogeneous processes with exceptional selectivity.

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Section: Resultsmentioning

confidence: 99%

Metal-organic frameworks as kinetic modulators for branched selectivity in hydroformylation

et al. 2020

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“…reported the coordination structure of FeBTC-MOF by EXAFS and XANES and confirmed that the unsaturated metal building units have Fe 3+ states. F. L. Morel et al 15 . reported the XANES spectra at P K-edge of phosphine and phosphine oxide functionalized framework materials to investigate their structural topology.…”

Section: Introductionmentioning

confidence: 99%

Investigation of Ionic Liquid interaction with ZnBDC-Metal Organic Framework through Scanning EXAFS and Inelastic Neutron Scattering

Dutta

Rao

Kumar

2019

Sci Rep

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Zn based Metal-Organic Framework (MOF), Zinc 1,4-benzenedicarboxylate (ZnBDC) has been synthesized and incorporated with ionic liquid (IL) 1-butyl-3 methylimidazolium bromide (BMIMBr) at optimum 50 wt% of IL. Interaction of BMIMBr in the micropores of ZnBDC-MOF is investigated by XPS, scanning EXAFS and inelastic neutron spectroscopy. Significant increase in binding energies of Zn spin-orbit peaks upon IL incorporation is observed from XPS spectra indicating motion of Br− anions of the IL BMIMBr towards the unsaturated Zn cluster of ZnBDC-MOF. The k-space periodicity as well as the local coordination geometry of Zn K-edge is investigated from the scanning EXAFS and XANES spectra. Asymmetric oscillation periodicity has been observed from the k-space scanning XANES spectra upon IL incorporation. Difference in peak positions of oxygen and zinc are observed from the R-space scanning EXAFS spectra suggesting change in coordination geometry due to dehydration of Zn2+ ion in the ZnBDC-MOF upon IL incorporation. Incorporation of IL in the pores of ZnBDC-MOF gives rise to increased scattering intensity in the Inelastic Neutron Scattering (INS) spectra, which is attributed to the displacement of IL ions in the MOF pores.

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“…A qualitative proof for the incorporation of multiple linkers is usually unproblematic and can be confirmed by IR spectroscopy, XPS, XAS, solid‐state NMR spectroscopy and in some cases by single‐crystal analysis ( D ) . Moreover, UV/Vis spectroscopy can be used to prove the incorporation of certain linkers and might be able to quantify the linker ratios for certain systems …”

Section: Mixed‐linker Metal–organic Frameworkmentioning

confidence: 99%

Synthetic Strategies and Structural Arrangements of Isoreticular Mixed‐Component Metal–Organic Frameworks

Bitzer

Kleist

2019

Chemistry A European J

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In recent years, the synthesis of mixed‐metal and mixed‐linker metal–organic frameworks with multiple metals and/or linker molecules combined in one framework has become a growing field of interest. These mixed‐component or multivariate metal–organic framework materials provide the possibility to introduce multiple functionalities inside one framework. The interaction of guest molecules with different functionalities in the same material is a promising approach in the fields of gas storage, separation, catalysis and drug delivery. Furthermore, the combination of different components may lead to synergistic effects that cannot be achieved otherwise. These mixed‐component approaches open up new pathways to an even larger range of possible customizations in the field of metal–organic frameworks.

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Phosphine and phosphine oxide groups in metal–organic frameworks detected by P K-edge XAS

Cited by 25 publications

References 33 publications

Metal-organic frameworks as kinetic modulators for branched selectivity in hydroformylation

Metal-organic frameworks as kinetic modulators for branched selectivity in hydroformylation

Investigation of Ionic Liquid interaction with ZnBDC-Metal Organic Framework through Scanning EXAFS and Inelastic Neutron Scattering

Synthetic Strategies and Structural Arrangements of Isoreticular Mixed‐Component Metal–Organic Frameworks

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