A computational study of alkane hydrogen-exchange reactions on zeolites

Xiaobo Zheng; Paul Blowers

doi:10.1016/j.molcata.2005.07.029

A computational study of alkane hydrogen-exchange reactions on zeolites

Xiaobo Zheng, Paul Blowers

Research output: Contribution to journal › Article › peer-review

19 Scopus citations

Abstract

In this work, quantum chemical methods were applied to study light alkane hydrogen-exchange reactions on a zeolite cluster, RH + H₃SiOAlH ₂(OH′)SiH₃ → RH′ + H₃Si(OH) AlH₂OSiH₃. Methane, ethane, propane, and butane reactions were investigated. The reactants, products, and transition state structures were optimized using the B3LYP density functional theory method and the final energies were calculated using CBS-QB3, a complete basis set composite energy method. The computed activation barriers ranged from 28.32 kcal/mol for secondary hydrogen exchange of butane to 33.53 kcal/mol for methane. The relationship between activation energy and deprotonation energy was also investigated and a linear correlation was proposed in this work.

Original language	English (US)
Pages (from-to)	18-25
Number of pages	8
Journal	Journal of Molecular Catalysis A: Chemical
Volume	242
Issue number	1-2
DOIs	https://doi.org/10.1016/j.molcata.2005.07.029
State	Published - Dec 1 2005

Keywords

Alkane
CBS method
Hydrogen exchange
Zeolite

ASJC Scopus subject areas

Catalysis
Process Chemistry and Technology
Physical and Theoretical Chemistry

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10.1016/j.molcata.2005.07.029

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title = "A computational study of alkane hydrogen-exchange reactions on zeolites",

abstract = "In this work, quantum chemical methods were applied to study light alkane hydrogen-exchange reactions on a zeolite cluster, RH + H3SiOAlH 2(OH′)SiH3 → RH′ + H3Si(OH) AlH2OSiH3. Methane, ethane, propane, and butane reactions were investigated. The reactants, products, and transition state structures were optimized using the B3LYP density functional theory method and the final energies were calculated using CBS-QB3, a complete basis set composite energy method. The computed activation barriers ranged from 28.32 kcal/mol for secondary hydrogen exchange of butane to 33.53 kcal/mol for methane. The relationship between activation energy and deprotonation energy was also investigated and a linear correlation was proposed in this work.",

keywords = "Alkane, CBS method, Hydrogen exchange, Zeolite",

author = "Xiaobo Zheng and Paul Blowers",

note = "Funding Information: This work was funded by the State of Arizona through the Office of the Vice President for Research at the University of Arizona. Supercomputer time was provided by the National Computational Science Alliance and used the NCSA HP/Convex Exemplar SPP-2000 at the University of Illinois at Urbana-Champaign. Part of the supercomputer time was provided by National Partnership for Advanced Computational Infrastructure and used the IBM pSeries 690 and pSeries 655 at Boston University. ",

year = "2005",

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doi = "10.1016/j.molcata.2005.07.029",

language = "English (US)",

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AU - Zheng, Xiaobo

AU - Blowers, Paul

N1 - Funding Information: This work was funded by the State of Arizona through the Office of the Vice President for Research at the University of Arizona. Supercomputer time was provided by the National Computational Science Alliance and used the NCSA HP/Convex Exemplar SPP-2000 at the University of Illinois at Urbana-Champaign. Part of the supercomputer time was provided by National Partnership for Advanced Computational Infrastructure and used the IBM pSeries 690 and pSeries 655 at Boston University.

PY - 2005/12/1

Y1 - 2005/12/1

N2 - In this work, quantum chemical methods were applied to study light alkane hydrogen-exchange reactions on a zeolite cluster, RH + H3SiOAlH 2(OH′)SiH3 → RH′ + H3Si(OH) AlH2OSiH3. Methane, ethane, propane, and butane reactions were investigated. The reactants, products, and transition state structures were optimized using the B3LYP density functional theory method and the final energies were calculated using CBS-QB3, a complete basis set composite energy method. The computed activation barriers ranged from 28.32 kcal/mol for secondary hydrogen exchange of butane to 33.53 kcal/mol for methane. The relationship between activation energy and deprotonation energy was also investigated and a linear correlation was proposed in this work.

AB - In this work, quantum chemical methods were applied to study light alkane hydrogen-exchange reactions on a zeolite cluster, RH + H3SiOAlH 2(OH′)SiH3 → RH′ + H3Si(OH) AlH2OSiH3. Methane, ethane, propane, and butane reactions were investigated. The reactants, products, and transition state structures were optimized using the B3LYP density functional theory method and the final energies were calculated using CBS-QB3, a complete basis set composite energy method. The computed activation barriers ranged from 28.32 kcal/mol for secondary hydrogen exchange of butane to 33.53 kcal/mol for methane. The relationship between activation energy and deprotonation energy was also investigated and a linear correlation was proposed in this work.

KW - Alkane

KW - CBS method

KW - Hydrogen exchange

KW - Zeolite

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JO - Journal of Molecular Catalysis A: Chemical

JF - Journal of Molecular Catalysis A: Chemical

IS - 1-2

ER -

A computational study of alkane hydrogen-exchange reactions on zeolites

Abstract

Keywords

ASJC Scopus subject areas

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