Computational study of the carbonyl-ene reaction of encapsulated formaldehyde in Na-FAU zeolite

Sangthong, Winyoo; Probst, Michael; Limtrakul, Jumras

doi:10.1016/j.molstruc.2005.03.020

Cited by 27 publications

(17 citation statements)

References 41 publications

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“…[38,45] Ther eaction product, 3-buten-1-ol, is used as am onomer in copolymerization reactions with polypropylene and as intermediate for tetrahydrofuran synthesis.A lternatively,t he dehydration of this Prins reaction product could provide an ew route for the production of 1,3-butadiene.Wannakao et al performed DFT calculations to investigate the reaction over metal-exchanged faujasite (FAU)z eolites.…”

Section: Angewandte Minireviewsmentioning

confidence: 99%

“…In contrast to the transformations discussed above,t he Prins reaction of propene with formaldehyde has been scarcely explored (Scheme 8). [38,45] Ther eaction product, 3buten-1-ol, is used as am onomer in copolymerization reactions with polypropylene and as intermediate for tetrahydrofuran synthesis.A lternatively,t he dehydration of this Prins reaction product could provide an ew route for the production of 1,3-butadiene.Wannakao et al performed DFT calculations to investigate the reaction over metal-exchanged faujasite (FAU)z eolites. [45a] It was shown that the nanocages of Na-FAU zeolites suppress self-polymerization and decomposition of formaldehyde without the formaldehyde losing its reactivity toward nucleophiles.…”

Section: Angewandte Minireviewsmentioning

confidence: 99%

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Metalloenzyme‐Like Zeolites as Lewis Acid Catalysts for CC Bond Formation

Vyver

Román‐Leshkov

2015

Angew Chem Int Ed

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The use of metalloenzyme-like zeolites as Lewis acid catalysts for C-C bond formation reactions has received increasing attention over the past few years. In particular, the observation of direct aldol condensation reactions enabled by hydrophobic zeolites with isolated framework metal sites has encouraged the development of catalytic approaches for producing chemicals from biomass-derived compounds. The discovery of new Diels-Alder cycloaddition/dehydration routes and experimental and computational studies of Lewis acid catalyzed carbonyl-ene reactions have given a further boost to this rapidly evolving field.

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Section: Angewandte Minireviewsmentioning

confidence: 99%

Section: Angewandte Minireviewsmentioning

confidence: 99%

Metalloenzyme‐Like Zeolites as Lewis Acid Catalysts for CC Bond Formation

Vyver

Román‐Leshkov

2015

Angew Chem Int Ed

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“…Due mainly to the large unit cell of the MFI zeolite, the use of periodic calculation is computationally too expensive and even impractical. Recently, hybrid methods such as the embedded cluster, 26,27,[38][39][40][41][42][43][44][45][46] QM-Pot [47][48][49] as well as the ONIOM methods [50][51][52][53][54][55][56][57][58][59] have been used for including the framework effects of zeolite with the benefit of the computational cost becoming economically feasible. In the ONIOM2 scheme, the MFI zeolite is represented by the 128T model which covers the nanometer-sized cavity that is the intersection of the main and sinusoidal channels and the location of the active site of MFI zeolite.…”

Section: Computational Detailsmentioning

confidence: 99%

Effect of the acidic strength on the vapor phase Beckmann rearrangement of cyclohexanone oxime over the MFI zeolite: an embedded ONIOM study

Sirijaraensre

Limtrakul

2009

Phys. Chem. Chem. Phys.

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The mechanism and energetic profile of the Beckmann rearrangement reaction of cyclohexanone oxime to epsilon-caprolactam catalyzed by the H-[Al]-MFI and H-[B]-MFI zeolites were investigated by both the bare cluster and the ONIOM models at the B3LYP/6-31G(d,p) and the B3LYP/6-31G(d,p):MNDO levels of theory, respectively. In order to improve the energetic properties and take into account the whole zeolite framework effect, single point calculations are undertaken at the embedded ONIOM2 schemes; MP2/6-311G(d,p):HF/6-31G(d) with an additional long-range electrostatic potential from the extended zeolite framework. The reaction mechanism of the Beckmann rearrangement over the acid site of zeolites consists of three steps: the 1,2 H shift, the rearrangement and the tautomerization. The activation energies for the Beckmann rearrangement of cyclohexanone oxime on the H-[Al]-MFI zeolite are calculated to be 31.46, 16.15 and 18.95 kcal mol(-1), for the first, second and third steps, respectively, whereas in the H-[B]-MFI zeolite, the energy barriers for each step of the reaction are 24.33, 7.46 and 20.43 kcal mol(-1), respectively. The rate-determining step of the reaction is the first step, which is the transformation from the N-ended cyclohexanone oxime adsorption complex and the O-ended one. These results signify the important role that the acid strength of zeolites plays in altering the energy profile of the reaction. The results further indicate that the weak Brønsted acid sites in the [B]-MFI zeolite could better catalyze the Beckmann rearrangement of cyclohexanone oxime than the strong acid sites in the [Al]-MFI zeolite, as compared with the quantitatively low activation energy of most steps. However, the turnover reaction of the H-[B]-MFI zeolite might be delayed by the quantitatively high desorption energy of the product as compared to the adsorption energy of the reactant.

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“…Zn-FER was inactive in the reaction due to rapid deactivation. Theoretical studies [15][16][17] have showed, that FAU zeolites also can be used as a catalyst in Prins reaction, however, activity of zeolites of this type is not experimentally studied to date. Among other zeolites, H-MOR was used for 2-methylbuta-1,3-diene synthesis catalyst [18], but it was never used for buta-1,3-diene synthesis.…”

Section: Introductionmentioning

confidence: 99%

Deactivation of Zeolite Catalysts in the Prins Reaction between Propene and Formaldehyde in the Liquid Phase

2021

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The Prins reaction between propene and formaldehyde was studied over H-BEA, H-FAU, H-MFI and H-MOR zeolites at 150 °C in liquid phase. It was found that the H-BEA sample is the most active and selective toward buta-1,3-diene; the H-MFI is a potential catalyst for 3-buten-1-ol synthesis, while H-FAU can be used for 4-methyl-1,3-dioxane production. It had been confirmed that zeolite textural and acidic properties influence catalyst behaviour: the acidic properties influence sample activity, while product distribution is controlled by pore volume and effective pore diameter. The sample’s deactivation process had been studied and the kinetic model of deactivation was proposed. It was shown that the deactivation rate for the H-MFI catalyst is four times greater than for the H-BEA catalyst, probably because its strong/weak acid sites ratio is much more high than for the H-BEA.

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Computational study of the carbonyl-ene reaction of encapsulated formaldehyde in Na-FAU zeolite

Cited by 27 publications

References 41 publications

Metalloenzyme‐Like Zeolites as Lewis Acid Catalysts for CC Bond Formation

Metalloenzyme‐Like Zeolites as Lewis Acid Catalysts for CC Bond Formation

Effect of the acidic strength on the vapor phase Beckmann rearrangement of cyclohexanone oxime over the MFI zeolite: an embedded ONIOM study

Deactivation of Zeolite Catalysts in the Prins Reaction between Propene and Formaldehyde in the Liquid Phase

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