Theoretical study of hydrogen abstraction mechanism from methanol by means of Cu3 cluster as a heterogeneous catalyst model

Yamı́n, Lázaro J.; Gómez, Manuel F.; Arrúa, Luis A.

doi:10.1016/j.theochem.2004.04.062

Cited by 10 publications

(18 citation statements)

References 19 publications

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“…40−43 Methanol conversion in the presence of Cu 3 clusters was also studied. 22 In this context, a comparative study on the transformation of methanol in the presence of different small mixed silicon clusters, including Si 2 H, Si 2 Li, Si 2 Na, Si 2 Cu, and Si 2 Ag, is performed. Through this study, we aim to provide a detailed mechanism for the methanol activation with the help of various triatomic silicon clusters and thereby suggest subsequent extensive searches for doped silicon clusters as good catalysts for activating methanol and other hydrogenated organic compounds.…”

Section: Introductionmentioning

confidence: 99%

Comparative Study of Methanol Activation by Different Small Mixed Silicon Clusters Si₂M with M = H, Li, Na, Cu, and Ag

2017

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High-accuracy quantum chemical calculations were carried out to study the mechanisms and catalytic abilities of various mixed silicon species Si 2 M with M = H, Li, Na, Cu, and Ag toward the first step of methanol activation reaction. Standard heats of formation of these small triatomic Si clusters were determined. Potential-energy profiles were constructed using the coupled-cluster theory with extrapolation to complete basis set CCSD(T)/CBS, and CCSD(T)/aug-cc-pVTZ-PP for Si 2 Cu and Si 2 Ag. The most stable complexes generated by the interaction of methanol with the mixed clusters Si 2 M possess low-spin states and mainly stem from an M–O connection in preference to Si–O interaction, except for the Si 2 H case. In two competitive pathways including O–H and C–H bond breakings, the cleavage of the O–H bond in the presence of all clusters studied becomes predominant. Of the mixed clusters Si 2 M considered, the dissociation pathways of both O–H and C–H bonds with Si 2 Li turns out to have the lowest energy barriers. The most remarkable finding is the absence of the overall energy barrier for the O–H cleavage with the assistance of Si 2 Li. The breaking of O–H and C–H bonds with the assistance of Si 2 H, Si 2 Li, and Si 2 Na is kinetically preferred with respect to the Si 2 Cu and Si 2 Ag cases, apart from the case of Si 2 Na for O–H cleavage. In comparison with other transition-metal clusters with the same size, such as Cu 3 , Pt 3 , and PtAu 2 , the energy barriers for the O–H bond activation in the presence of small Si species, especially Si 2 H and Si 2 Li, are found to be lower. Consequently, these small mixed silicon clusters can be regarded as promising alternatives for the expensive metal-based catalysts currently used for methanol activation particularly and other dehydrogenation processes of organic compounds. The present study also suggests a further extensive search for other doped silicon clusters as efficient and more realistic gas-phase catalysts for important dehydrogenation processes in such a way that they can be experimentally prepared and implemented.

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Section: Introductionmentioning

confidence: 99%

Comparative Study of Methanol Activation by Different Small Mixed Silicon Clusters Si₂M with M = H, Li, Na, Cu, and Ag

2017

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“…Maybe the most important disadvantage of this approach is the use of pseudopotentials to describe bond breaking and forming in the reacting species. If we reduce the metal surface to a small cluster, we can apply a full electron treatment to the reacting species, whereas pseudopotentials are reserved only for metal atoms [24][25][26].…”

Section: Validation Of the Cluster Calculationsmentioning

confidence: 99%

Insights into ethanol decomposition over Pt: A DFT energy decomposition analysis for the reaction mechanism leading to C2H6 and CH4

Dancini-Pontes

Fernandes-Machado

Souza

et al. 2015

Applied Catalysis A: General

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“…Reducing the size of cluster can accelerate catalyzed ability, because nanosized cluster can produce tremendous improvements in catalyzed performance due to its large surface area . Up to now, numerous experimental and theoretical studies focused on the cluster catalysts for methanol dissociation . Binary metal clusters have unique characters due to their unique structures.…”

Section: Introductionmentioning

confidence: 99%

“…[40][41][42] Up to now, numerous experimental and theoretical studies focused on the cluster catalysts for methanol dissociation. [39,[43][44][45][46][47] Binary metal clusters have unique characters due to their unique structures. The electronic, magnetic, and reactivity properties will change with the number of atoms and composition.…”

Section: Introductionmentioning

confidence: 99%

Methanol activation catalyzed by Pt₇, Pt₃Cu₄, and Cu₇ clusters: A density functional theory investigation

Wei

Feng

Liu

et al. 2017

Applied Organom Chemis

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Metal clusters were considered as excellent catalysts for methanol dissociation. In this work, two main decomposition mechanisms of methanol on Pt7, Pt3Cu4, and Cu7 clusters were investigated by the density functional theory. One was methanol direct dehydrogenation, and the other was non‐CO‐involved oxidation. Stable adsorption configurations, elementary reaction barriers, the potential energy surface (PES), and the charge analysis were elucidated. The results showed that on Pt7 cluster, methanol was favorable for direct decomposition. On Pt3Cu4 and Cu7 clusters, methanol was inclined to the pathway of non‐CO‐involved oxidation. All the transition‐state energies and the final‐state energies were related in a linear, including those for the clusters. The results may be useful for computational design and catalysts optimization.

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Theoretical study of hydrogen abstraction mechanism from methanol by means of Cu3 cluster as a heterogeneous catalyst model

Cited by 10 publications

References 19 publications

Comparative Study of Methanol Activation by Different Small Mixed Silicon Clusters Si₂M with M = H, Li, Na, Cu, and Ag

Comparative Study of Methanol Activation by Different Small Mixed Silicon Clusters Si₂M with M = H, Li, Na, Cu, and Ag

Insights into ethanol decomposition over Pt: A DFT energy decomposition analysis for the reaction mechanism leading to C2H6 and CH4

Methanol activation catalyzed by Pt₇, Pt₃Cu₄, and Cu₇ clusters: A density functional theory investigation

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Theoretical study of hydrogen abstraction mechanism from methanol by means of Cu3 cluster as a heterogeneous catalyst model

Cited by 10 publications

References 19 publications

Comparative Study of Methanol Activation by Different Small Mixed Silicon Clusters Si2M with M = H, Li, Na, Cu, and Ag

Comparative Study of Methanol Activation by Different Small Mixed Silicon Clusters Si2M with M = H, Li, Na, Cu, and Ag

Insights into ethanol decomposition over Pt: A DFT energy decomposition analysis for the reaction mechanism leading to C2H6 and CH4

Methanol activation catalyzed by Pt7, Pt3Cu4, and Cu7 clusters: A density functional theory investigation

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Comparative Study of Methanol Activation by Different Small Mixed Silicon Clusters Si₂M with M = H, Li, Na, Cu, and Ag

Comparative Study of Methanol Activation by Different Small Mixed Silicon Clusters Si₂M with M = H, Li, Na, Cu, and Ag

Methanol activation catalyzed by Pt₇, Pt₃Cu₄, and Cu₇ clusters: A density functional theory investigation