Metal–organic frameworks as heterogeneous catalysts for oxidation reactions

Dhakshinamoorthy, Amarajothi; Álvaro, Mercedes; Garcı́a, Hermenegildo

doi:10.1039/c1cy00068c

Cited by 285 publications

(154 citation statements)

References 86 publications

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“…Especially, MOFs behave as semiconductors when exposed to light, thus making MOFs potentially be heterogeneous photocatalysts for environmental purification due to their high crystallinity with well-defined pore properties, high specific surface area and tailorable structures [11][12][13][14]. Garcia et al firstly…”

Section: Introductionmentioning

confidence: 99%

TiO2 encapsulated in Salicylaldehyde-NH2-MIL-101(Cr) for enhanced visible light-driven photodegradation of MB

Xia

et al. 2016

Applied Catalysis B: Environmental

201

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Section: Introductionmentioning

confidence: 99%

TiO2 encapsulated in Salicylaldehyde-NH2-MIL-101(Cr) for enhanced visible light-driven photodegradation of MB

Xia

et al. 2016

Applied Catalysis B: Environmental

201

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“…Notably, a wide scope of MOF applications in catalysis is enabled by the high specific surface area and the ability to regulate their porosity by modification of both organic ligands and transition metals. The role of MOFs in the field of catalysis has been discussed in various reviews [12][13][14][15][16][17][18]. One of the most widely investigated MOFs from the plethora of known frameworks is the Zr(IV)-terephthalate MOF designated as UiO-66, which has received considerable attention over the past years [19][20][21].…”

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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“…MFU-1 showed a cyclohexene conversion of 22.5% after 22 h of reaction (theoretically maximum 50% conversion), with tert-butyl-2-cyclohexenyl-1-peroxide as the main product (66% selectivity). Garcia et al recently published a review on the use of MOFs as oxidation catalysts 29 . Recent studies by us 30 have focused on the catalytic performance of a saturated vanadium MOF, namely MIL-47 (V IV O(CO 2 -C 6 H 4 -CO 2 ) 31 .…”

Section: Introductionmentioning

confidence: 99%

The coordinatively saturated vanadium MIL-47 as a low leaching heterogeneous catalyst in the oxidation of cyclohexene

Leus

Vandichel

Liu

et al. 2012

Journal of Catalysis

101

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A Metal Organic Framework, containing coordinatively saturated V +IV sites linked together by terephthalic linkers (V-MIL-47) is evaluated as a catalyst in the epoxidation of cyclohexene. Different solvents and conditions are tested and compared. If the oxidant TBHP is dissolved in water, a significant leaching of V-species into the solution is observed and also radical pathways are 2 prominently operative leading to the formation of an adduct between the peroxide and cyclohexene. If however the oxidant is dissolved in decane, leaching is negligible and the structural integrity of the V-MIL-47 is maintained during successive runs. The selectivity towards the epoxide is very high in these circumstances. Extensive computational modelling is performed to show that several reaction cycles are possible. EPR and NMR measurements confirm that at least two parallel catalytic cycles are co-existing: one with V +IV sites and one with pre-oxidized V +V sites, and this in complete agreement with the theoretical predictions.

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Metal–organic frameworks as heterogeneous catalysts for oxidation reactions

Cited by 285 publications

References 86 publications

TiO2 encapsulated in Salicylaldehyde-NH2-MIL-101(Cr) for enhanced visible light-driven photodegradation of MB

TiO2 encapsulated in Salicylaldehyde-NH2-MIL-101(Cr) for enhanced visible light-driven photodegradation of MB

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

The coordinatively saturated vanadium MIL-47 as a low leaching heterogeneous catalyst in the oxidation of cyclohexene

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