QM/MM study of the reactivity of zeolite bound methoxy and carbene groups

Nastase, Stefan A. F.; Logsdail, Andrew J.; Catlow, C. Richard A.

doi:10.1039/d1cp02535j

Cited by 15 publications

(16 citation statements)

References 75 publications

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“…Furthermore, Dass and colleagues also came to a similar conclusion after investigations on methanol–propane interactions over ZSM-5. Besides these experimental approaches, computational chemists have also focused on the formation and stabilization of carbenes in zeolite catalyzed MTH reactions. − Overall, computational studies revealed that it is energy demanding to form carbenes from surface methoxy groups; however, its bonding on the zeolite framework is strong enough to remain stable to further react with other molecules. Furthermore, they are less likely to participate in gas-phase reactions.…”

Section: Carbene Chemistry In Zeolite Catalysismentioning

confidence: 99%

First-Generation Organic Reaction Intermediates in Zeolite Chemistry and Catalysis

Gong

Çağlayan

et al. 2022

Chem. Rev.

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Zeolite chemistry and catalysis are expected to play a decisive role in the next decade(s) to build a more decentralized renewable feedstock-dependent sustainable society owing to the increased scrutiny over carbon emissions. Therefore, the lack of fundamental and mechanistic understanding of these processes is a critical “technical bottleneck” that must be eliminated to maximize economic value and minimize waste. We have identified, considering this objective, that the chemistry related to the first-generation reaction intermediates (i.e., carbocations, radicals, carbenes, ketenes, and carbanions) in zeolite chemistry and catalysis is highly underdeveloped or undervalued compared to other catalysis streams (e.g., homogeneous catalysis). This limitation can often be attributed to the technological restrictions to detect such “short-lived and highly reactive” intermediates at the interface (gas–solid/solid–liquid); however, the recent rise of sophisticated spectroscopic/analytical techniques (including under in situ/operando conditions) and modern data analysis methods collectively compete to unravel the impact of these organic intermediates. This comprehensive review summarizes the state-of-the-art first-generation organic reaction intermediates in zeolite chemistry and catalysis and evaluates their existing challenges and future prospects, to contribute significantly to the “circular carbon economy” initiatives.

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Section: Carbene Chemistry In Zeolite Catalysismentioning

confidence: 99%

First-Generation Organic Reaction Intermediates in Zeolite Chemistry and Catalysis

Gong

Çağlayan

et al. 2022

Chem. Rev.

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“…In our calculation, the methoxonium ion has been formed as the precursor of possible various chemicals such as olefins and light hydrocarbons. Previous studies have also confirmed that such ionic species might occur during the interaction of methanol and the Brönsted acid sites of zeolite such as in MFI and ZSM-5 [14,15]. Additional several studies are listed in Table 1 regarding the interaction between methanol and zeolite.…”

Section: (B)mentioning

confidence: 76%

“…However, the used of zeolite as heterogenous catalyst is one of the most important aspects in zeolite application. The computational studies on the catalytic activity of zeolite towards methanol transformation have been reported highlighting the complex reaction that might occur due to simple interaction between methanol and zeolite [14,15]. Most of the studies are utilizing first principle calculation, such as density functional theory as well as modelling through classical molecular dynamics.…”

Section: Introductionmentioning

confidence: 99%

Investigating the Interaction between Methanol and the Heulandite-type Zeolite using First Principle Molecular Dynamic

Wulandhani

Pambudi

2022

Bull. Chem. React. Eng. Catal.

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The interaction between methanol and the Heulandite-type zeolite has been unveiled to give an atomic scale detail regarding the catalytic activity of this zeolite for methanol conversion. The study was carried out by first principle molecular dynamics to get an insight into the structure and electronic behaviour of methanol inside the zeolite structure at different temperatures. The behaviour of methanol was studied when the location of the proton of Bronsted acid sites was varied to give both possible direct and less interaction with methanol. The results show that methanol interacts with the proton from zeolite to give a cationic species of [CH3OH2]+ both in 300K and 573K conditions. However, when the proton is located at different location far from possible interaction with methanol, the formation of a cationic species is hindered. This study provides an insight into the design of Heulandite type zeolite to give a catalytic activity toward methanol transformation.

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“…Scheme 4 envisages insertion of a carbene formed by SMS deprotonation into the CH bond of an adjacent SMS to form ethoxide, occurring in a concerted manner rather than step-wise. 72…”

Section: Resultsmentioning

confidence: 99%

Carbene-like reactivity of methoxy groups in a single crystal SAPO-34 MTO catalyst

Minova

Bühl

Matam

et al. 2022

Catal. Sci. Technol.

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QM/MM study of the reactivity of zeolite bound methoxy and carbene groups

Abstract: The conversion of methanol-to-hydrocarbons (MTH) is known to occur via an autocatalytic process in zeolites, where framework-bound methoxy species play a pivotal role, especially during catalyst induction. Recent NMR and...

Cited by 15 publications

References 75 publications

First-Generation Organic Reaction Intermediates in Zeolite Chemistry and Catalysis

First-Generation Organic Reaction Intermediates in Zeolite Chemistry and Catalysis

Investigating the Interaction between Methanol and the Heulandite-type Zeolite using First Principle Molecular Dynamic

Carbene-like reactivity of methoxy groups in a single crystal SAPO-34 MTO catalyst

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