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Oxidation of lower alkenes by Α-oxygen (FeIII–O•−)Α on the FeZSM-5 surface: The epoxidation or the allylic oxidation? / Starokon, Eugeny V.; Malykhin, Sergei E.; Parfenov, Mikhail V. et al.

In: Molecular Catalysis, Vol. 443, 01.12.2017, p. 43-51.

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Starokon EV, Malykhin SE, Parfenov MV, Zhidomirov GM, Kharitonov AS. Oxidation of lower alkenes by Α-oxygen (FeIII–O•−)Α on the FeZSM-5 surface: The epoxidation or the allylic oxidation? Molecular Catalysis. 2017 Dec 1;443:43-51. doi: 10.1016/j.mcat.2017.09.017

Author

Starokon, Eugeny V. ; Malykhin, Sergei E. ; Parfenov, Mikhail V. et al. / Oxidation of lower alkenes by Α-oxygen (FeIII–O•−)Α on the FeZSM-5 surface: The epoxidation or the allylic oxidation?. In: Molecular Catalysis. 2017 ; Vol. 443. pp. 43-51.

BibTeX

@article{67028ee9910740bfafbcfb87fb2aefee,
title = "Oxidation of lower alkenes by Α-oxygen (FeIII–O•−)Α on the FeZSM-5 surface: The epoxidation or the allylic oxidation?",
abstract = "Reactions of anion-radical α-oxygen (FeIII–O•−)α with propylene and 1-butene on sodium-modified FeZSM-5 zeolites were studied in the temperature range from −60 to 25 °C. Products were extracted from the zeolite surface and identified. It was found that main reaction pathway was the epoxides formation. Selectivity for epoxides at −60 °C was 59–64%. Other products were formed as a result of secondary transformations of epoxides on the zeolite surface. According to IR spectroscopy, the oxidation of propylene over the entire temperature range and 1-butene at −60 °C were not accompanied by the formation of (FeIII–OH)α groups, in distinction to methane oxidation. This testifies that hydrogen abstraction does not occur. In case of 1-butene reaction with α-oxygen at 25 °C, hydrogen abstraction occurred but was insignificant, ca 7%. According to DFT calculation ferraoxetane intermediate formation is preferable over hydrogen abstraction. Following decomposition of this intermediate leads to the propylene oxide (PO) formation. The results may be relevant to the low selectivity problem of the silver catalyst in propylene epoxidation and raise doubts about the presently accepted mechanism explaining an adverse effect of allylic hydrogen.",
keywords = "DFT, NO oxidant, Oxygen anion radicals, Propylene epoxidation, α-oxygen, GAS-PHASE EPOXIDATION, PROPYLENE EPOXIDATION, ACTIVE-SITES, ANION-RADICALS, alpha-oxygen, NITROUS-OXIDE, IRON-OXIDE, METHANE, N2O oxidant, ETHYLENE EPOXIDATION, N2O DECOMPOSITION, DENSITY-FUNCTIONAL THEORY",
author = "Starokon, {Eugeny V.} and Malykhin, {Sergei E.} and Parfenov, {Mikhail V.} and Zhidomirov, {Georgy M.} and Kharitonov, {Alexander S.}",
note = "Publisher Copyright: {\textcopyright} 2017 Elsevier B.V.",
year = "2017",
month = dec,
day = "1",
doi = "10.1016/j.mcat.2017.09.017",
language = "English",
volume = "443",
pages = "43--51",
journal = "Molecular Catalysis",
issn = "2468-8231",
publisher = "Elsevier",

}

RIS

TY - JOUR

T1 - Oxidation of lower alkenes by Α-oxygen (FeIII–O•−)Α on the FeZSM-5 surface: The epoxidation or the allylic oxidation?

AU - Starokon, Eugeny V.

AU - Malykhin, Sergei E.

AU - Parfenov, Mikhail V.

AU - Zhidomirov, Georgy M.

AU - Kharitonov, Alexander S.

N1 - Publisher Copyright: © 2017 Elsevier B.V.

PY - 2017/12/1

Y1 - 2017/12/1

N2 - Reactions of anion-radical α-oxygen (FeIII–O•−)α with propylene and 1-butene on sodium-modified FeZSM-5 zeolites were studied in the temperature range from −60 to 25 °C. Products were extracted from the zeolite surface and identified. It was found that main reaction pathway was the epoxides formation. Selectivity for epoxides at −60 °C was 59–64%. Other products were formed as a result of secondary transformations of epoxides on the zeolite surface. According to IR spectroscopy, the oxidation of propylene over the entire temperature range and 1-butene at −60 °C were not accompanied by the formation of (FeIII–OH)α groups, in distinction to methane oxidation. This testifies that hydrogen abstraction does not occur. In case of 1-butene reaction with α-oxygen at 25 °C, hydrogen abstraction occurred but was insignificant, ca 7%. According to DFT calculation ferraoxetane intermediate formation is preferable over hydrogen abstraction. Following decomposition of this intermediate leads to the propylene oxide (PO) formation. The results may be relevant to the low selectivity problem of the silver catalyst in propylene epoxidation and raise doubts about the presently accepted mechanism explaining an adverse effect of allylic hydrogen.

AB - Reactions of anion-radical α-oxygen (FeIII–O•−)α with propylene and 1-butene on sodium-modified FeZSM-5 zeolites were studied in the temperature range from −60 to 25 °C. Products were extracted from the zeolite surface and identified. It was found that main reaction pathway was the epoxides formation. Selectivity for epoxides at −60 °C was 59–64%. Other products were formed as a result of secondary transformations of epoxides on the zeolite surface. According to IR spectroscopy, the oxidation of propylene over the entire temperature range and 1-butene at −60 °C were not accompanied by the formation of (FeIII–OH)α groups, in distinction to methane oxidation. This testifies that hydrogen abstraction does not occur. In case of 1-butene reaction with α-oxygen at 25 °C, hydrogen abstraction occurred but was insignificant, ca 7%. According to DFT calculation ferraoxetane intermediate formation is preferable over hydrogen abstraction. Following decomposition of this intermediate leads to the propylene oxide (PO) formation. The results may be relevant to the low selectivity problem of the silver catalyst in propylene epoxidation and raise doubts about the presently accepted mechanism explaining an adverse effect of allylic hydrogen.

KW - DFT

KW - NO oxidant

KW - Oxygen anion radicals

KW - Propylene epoxidation

KW - α-oxygen

KW - GAS-PHASE EPOXIDATION

KW - PROPYLENE EPOXIDATION

KW - ACTIVE-SITES

KW - ANION-RADICALS

KW - alpha-oxygen

KW - NITROUS-OXIDE

KW - IRON-OXIDE

KW - METHANE

KW - N2O oxidant

KW - ETHYLENE EPOXIDATION

KW - N2O DECOMPOSITION

KW - DENSITY-FUNCTIONAL THEORY

UR - http://www.scopus.com/inward/record.url?scp=85033391527&partnerID=8YFLogxK

U2 - 10.1016/j.mcat.2017.09.017

DO - 10.1016/j.mcat.2017.09.017

M3 - Article

AN - SCOPUS:85033391527

VL - 443

SP - 43

EP - 51

JO - Molecular Catalysis

JF - Molecular Catalysis

SN - 2468-8231

ER -

ID: 9409613