A kinetic study of vapor-phase cyclohexene epoxidation by H2O2 over mesoporous TS-1

Stephanie Kwon; Neil M. Schweitzer; Sunyoung Park; Peter C. Stair; Randall Q. Snurr

doi:10.1016/j.jcat.2015.04.005

A kinetic study of vapor-phase cyclohexene epoxidation by H₂O₂ over mesoporous TS-1

Stephanie Kwon, Neil M. Schweitzer, Sunyoung Park, Peter C. Stair^*, Randall Q. Snurr

^*Corresponding author for this work

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

49 Scopus citations

Abstract

A kinetic analysis of gas-phase cyclohexene epoxidation by H₂O₂ over mesoporous TS-1 was performed. The production of cyclohexene oxide was very stable with high selectivity. Based on the kinetic analysis, the gas-phase mechanism is proposed to be similar to that of the liquid-phase reaction: an Eley-Rideal type mechanism, in which the reaction between a Ti-OOH intermediate and the physisorbed alkene is the rate-determining step. When the partial pressure of water or H₂O₂ was varied, a compensation effect was observed. Based on the kinetic model, the compensation effect is attributed to variations in the surface coverage of intermediates, specifically the competitive adsorption of water and H₂O₂ at the Ti active sites. A meaningful activation energy can only be obtained at high surface coverages of H₂O₂ and was determined to be 40 ± 2 kJ/mol.

Original language	English (US)
Pages (from-to)	107-115
Number of pages	9
Journal	Journal of Catalysis
Volume	326
DOIs	https://doi.org/10.1016/j.jcat.2015.04.005
State	Published - Jun 1 2015

Keywords

Alkene
Compensation effect
Hydrogen peroxide
Oxidation
Zeolite

ASJC Scopus subject areas

Catalysis
Physical and Theoretical Chemistry

Access to Document

10.1016/j.jcat.2015.04.005

Cite this

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title = "A kinetic study of vapor-phase cyclohexene epoxidation by H2O2 over mesoporous TS-1",

abstract = "A kinetic analysis of gas-phase cyclohexene epoxidation by H2O2 over mesoporous TS-1 was performed. The production of cyclohexene oxide was very stable with high selectivity. Based on the kinetic analysis, the gas-phase mechanism is proposed to be similar to that of the liquid-phase reaction: an Eley-Rideal type mechanism, in which the reaction between a Ti-OOH intermediate and the physisorbed alkene is the rate-determining step. When the partial pressure of water or H2O2 was varied, a compensation effect was observed. Based on the kinetic model, the compensation effect is attributed to variations in the surface coverage of intermediates, specifically the competitive adsorption of water and H2O2 at the Ti active sites. A meaningful activation energy can only be obtained at high surface coverages of H2O2 and was determined to be 40 ± 2 kJ/mol.",

keywords = "Alkene, Compensation effect, Hydrogen peroxide, Oxidation, Zeolite",

author = "Stephanie Kwon and Schweitzer, {Neil M.} and Sunyoung Park and Stair, {Peter C.} and Snurr, {Randall Q.}",

note = "Funding Information: The CleanCat Core Facility acknowledges funding from the Department of Energy (DE-SC0001329) used for the purchase of the vapor phase reactor system and analytics. This work made use of the J.B. Cohen X-Ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR-1121262) at the Materials Research Center of Northwestern University. We acknowledge support of the Institute for Catalysis in Energy Processes from the Chemical Sciences, Geosciences, and Biosciences Division , Office of BES , Office of Science , U.S. DOE Grant DE-FG-02-03ER15457 . Publisher Copyright: {\textcopyright} 2015 Elsevier B.V. All rights reserved.",

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doi = "10.1016/j.jcat.2015.04.005",

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AU - Kwon, Stephanie

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AU - Stair, Peter C.

AU - Snurr, Randall Q.

N1 - Funding Information: The CleanCat Core Facility acknowledges funding from the Department of Energy (DE-SC0001329) used for the purchase of the vapor phase reactor system and analytics. This work made use of the J.B. Cohen X-Ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR-1121262) at the Materials Research Center of Northwestern University. We acknowledge support of the Institute for Catalysis in Energy Processes from the Chemical Sciences, Geosciences, and Biosciences Division , Office of BES , Office of Science , U.S. DOE Grant DE-FG-02-03ER15457 . Publisher Copyright: © 2015 Elsevier B.V. All rights reserved.

PY - 2015/6/1

Y1 - 2015/6/1

N2 - A kinetic analysis of gas-phase cyclohexene epoxidation by H2O2 over mesoporous TS-1 was performed. The production of cyclohexene oxide was very stable with high selectivity. Based on the kinetic analysis, the gas-phase mechanism is proposed to be similar to that of the liquid-phase reaction: an Eley-Rideal type mechanism, in which the reaction between a Ti-OOH intermediate and the physisorbed alkene is the rate-determining step. When the partial pressure of water or H2O2 was varied, a compensation effect was observed. Based on the kinetic model, the compensation effect is attributed to variations in the surface coverage of intermediates, specifically the competitive adsorption of water and H2O2 at the Ti active sites. A meaningful activation energy can only be obtained at high surface coverages of H2O2 and was determined to be 40 ± 2 kJ/mol.

AB - A kinetic analysis of gas-phase cyclohexene epoxidation by H2O2 over mesoporous TS-1 was performed. The production of cyclohexene oxide was very stable with high selectivity. Based on the kinetic analysis, the gas-phase mechanism is proposed to be similar to that of the liquid-phase reaction: an Eley-Rideal type mechanism, in which the reaction between a Ti-OOH intermediate and the physisorbed alkene is the rate-determining step. When the partial pressure of water or H2O2 was varied, a compensation effect was observed. Based on the kinetic model, the compensation effect is attributed to variations in the surface coverage of intermediates, specifically the competitive adsorption of water and H2O2 at the Ti active sites. A meaningful activation energy can only be obtained at high surface coverages of H2O2 and was determined to be 40 ± 2 kJ/mol.

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KW - Compensation effect

KW - Hydrogen peroxide

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KW - Zeolite

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