A density-functional study of the dehydrogenation reaction of isobutane over zeolites

Milas, Ivan; Nascimento, Marco Antônio Chaer

doi:10.1016/s0009-2614(01)00227-5

Cited by 40 publications

(26 citation statements)

References 23 publications

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“…Numerous studies published since the early 2000 s [122][123][124][125][126][127][128][129][130] have demonstrated that long-range electrostatic interactions are critical not only for accurately capturing experimentally measured activation barriers, but also for providing a complete picture of transition state structures involved in catalysis. One such seminal study on the impact of long-range electrostatics on the calculated activation barrier for alkane cracking in zeolites was conducted by Zygmunt and coworkers [122].…”

Section: Impact Of Long-range Electrostaticsmentioning

confidence: 99%

“…These results provided early evidence that the TS structures for the cracking of alkanes on H-MFI are especially sensitive to long-range electrostatic effects. In later studies [124][125][126] by Nascimento and coworkers, the dehydrogenation and cracking of isobutane over HZSM-5 were both examined at the B3LYP/6-31G(d,p) level. Activation energies predicted for T5 and T20 clusters were found to differ by up to 12 kcal/mol.…”

Section: Impact Of Long-range Electrostaticsmentioning

confidence: 99%

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Impact of long-range electrostatic and dispersive interactions on theoretical predictions of adsorption and catalysis in zeolites

et al. 2018

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In this paper, we review the importance of long-range zeolite framework interactions in theoretical predictions for a variety of zeolite-catalyzed processes, and we show why such interactions must be determined accurately in order to reproduce experimentally measured adsorption and activation energies. We begin with an overview of the different strategies that have been used to account for long-range coulombic and dispersive interactions of zeolite framework atoms with species adsorbed at an active site. These methods include full periodic-DFT calculations and multi-layer hybrid techniques. Electrostatic interactions are observed to have a more significant impact than dispersive interactions on the geometries of ion-pair transition states and adsorbed species. Stabilization of the TS relative to reactant complexes is also dictated by electrostatic interactions. Dispersion effects are found to significantly stabilize both transition and reactant states for adsorbed species, especially those which have dimensions that provide good fits within the zeolite pore or cavity. We also show that the relevance of particular active site configurations can be missed, if the effects of long-range interactions are neglected. As a case in point, we demonstrate that a site previously considered inactive for ethane dehydrogenation, [GaH 2 ] + may in fact be more active than previously thought, when the impact of long-range interactions on the predicted activation energy is taken into account. Finally, the use of hybrid quantum mechanics/molecular mechanics approaches on extended, finite zeolite clusters has emerged as an accurate, highly cost-effective, and versatile alternative towards overcoming some of the present-day limitations of periodic calculations.

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Section: Impact Of Long-range Electrostaticsmentioning

confidence: 99%

Section: Impact Of Long-range Electrostaticsmentioning

confidence: 99%

Impact of long-range electrostatic and dispersive interactions on theoretical predictions of adsorption and catalysis in zeolites

et al. 2018

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“…The results suggested that the T9 and T10 are thermodynamically the more stables sites. Milas and Nascimento studied the interaction of isobutane with zeolites using DFT-B3LYP on a 5T [65] and a double-ring 20T clusters [66]. The results show that the activation energy decreases with increasing cluster size.…”

Section: Ab Initio Methods In Catalysismentioning

confidence: 99%

Application of computational methods to catalytic systems

Ruette

Sanchéz²,

Sierraalta

et al. 2005

Journal of Molecular Catalysis A: Chemical

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“…It is well-known that the dehydrogenation and cracking of alkane are assumed to proceed through carbonium-ion intermediates [51][52][53]. For Ni 2 P-ADC catalysts, the partial positive charges carried on Ni surface (Ni ␦+ ) in Ni 2 P-ADC catalysts resulted from electron transfer from Ni to P in nickel phosphide [54,55] is a key factor for the enhancing selectivity, which can obviously decrease the strength of Ni-C bond as well as the ability of dehydrogenation, which improves the selectivity of isobutane dehydrogenation.…”

Section: Catalytic Performance For Isobutane Dehydrogenationmentioning

confidence: 99%

Novel preparation of highly dispersed Ni2P embedded in carbon framework and its improved catalytic performance

Wang

2016

Applied Surface Science

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A density-functional study of the dehydrogenation reaction of isobutane over zeolites

Cited by 40 publications

References 23 publications

Impact of long-range electrostatic and dispersive interactions on theoretical predictions of adsorption and catalysis in zeolites

Impact of long-range electrostatic and dispersive interactions on theoretical predictions of adsorption and catalysis in zeolites

Application of computational methods to catalytic systems

Novel preparation of highly dispersed Ni2P embedded in carbon framework and its improved catalytic performance

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