Hydrogen pressure dependence in the ring opening of methyloxirane over silica-supported Pd and Rh catalysts

Effect of high temperature on ring-opening routes

I. Pálinkó, József Ocskó

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

The high-temperature ring-opening reactions of methyloxirane were investigated with or without added hydrogen over silicasupported Pd and Rh catalysts. Without added hydrogen, mainly isomerization occurred, giving acetone through the rupture of the sterically less hindered C-O bond (route b). With added hydrogen, hydrogenative ring opening also took place and the sterically more hindered C-O bond was broken as well (route a). At 473 K allyl alcohol was formed too: a product not found at lower temperatures. Since route a was predominant over both catalysts, a bifunctional mechanism had to be considered. It is known that methyloxirane adsorbs irreversibly, therefore the shape of product formation rate vs. hydrogen pressure curves could be used for mechanistic considerations.

Original languageEnglish
Pages (from-to)261-265
Number of pages5
JournalJournal of Molecular Catalysis A: Chemical
Volume104
Issue number3
Publication statusPublished - 1996

Fingerprint

Silicon Dioxide
pressure dependence
Hydrogen
Silica
routes
silicon dioxide
catalysts
Catalysts
rings
hydrogen
Temperature
products
Isomerization
Acetone
acetone
isomerization
alcohols
Alcohols
propylene oxide
curves

Keywords

  • High temperature effects
  • Hydrogen
  • Methyloxirane
  • Palladium
  • Pressure dependence
  • Rhodium
  • Ring-opening reactions
  • Silica
  • Supported catalysts

ASJC Scopus subject areas

  • Catalysis
  • Process Chemistry and Technology

Cite this

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abstract = "The high-temperature ring-opening reactions of methyloxirane were investigated with or without added hydrogen over silicasupported Pd and Rh catalysts. Without added hydrogen, mainly isomerization occurred, giving acetone through the rupture of the sterically less hindered C-O bond (route b). With added hydrogen, hydrogenative ring opening also took place and the sterically more hindered C-O bond was broken as well (route a). At 473 K allyl alcohol was formed too: a product not found at lower temperatures. Since route a was predominant over both catalysts, a bifunctional mechanism had to be considered. It is known that methyloxirane adsorbs irreversibly, therefore the shape of product formation rate vs. hydrogen pressure curves could be used for mechanistic considerations.",
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N2 - The high-temperature ring-opening reactions of methyloxirane were investigated with or without added hydrogen over silicasupported Pd and Rh catalysts. Without added hydrogen, mainly isomerization occurred, giving acetone through the rupture of the sterically less hindered C-O bond (route b). With added hydrogen, hydrogenative ring opening also took place and the sterically more hindered C-O bond was broken as well (route a). At 473 K allyl alcohol was formed too: a product not found at lower temperatures. Since route a was predominant over both catalysts, a bifunctional mechanism had to be considered. It is known that methyloxirane adsorbs irreversibly, therefore the shape of product formation rate vs. hydrogen pressure curves could be used for mechanistic considerations.

AB - The high-temperature ring-opening reactions of methyloxirane were investigated with or without added hydrogen over silicasupported Pd and Rh catalysts. Without added hydrogen, mainly isomerization occurred, giving acetone through the rupture of the sterically less hindered C-O bond (route b). With added hydrogen, hydrogenative ring opening also took place and the sterically more hindered C-O bond was broken as well (route a). At 473 K allyl alcohol was formed too: a product not found at lower temperatures. Since route a was predominant over both catalysts, a bifunctional mechanism had to be considered. It is known that methyloxirane adsorbs irreversibly, therefore the shape of product formation rate vs. hydrogen pressure curves could be used for mechanistic considerations.

KW - High temperature effects

KW - Hydrogen

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