Microkinetic analysis of ring opening and decarboxylation of γ-valerolactone over silica alumina

Jesse Quentin Bond, Christian S. Jungong, Anargyros Chatzidimitriou

Research output: Contribution to journalArticle

19 Scopus citations

Abstract

This study considers the thermochemistry and kinetics of γ-valerolactone and pentenoic acid interconversion as well as the decarboxylation of both molecules over amorphous silica alumina. Through microkinetic analysis, macroscopically observed production rates and product distributions are reconciled with a mechanistic description of all chemistries. Ring opening of γ-valerolactone, cyclization of pentenoic acids, and decarboxylation of either molecule occur in parallel at surface Brønsted sites through a sequence of proton-mediated elementary steps. Conceptually, this is illustrated as proceeding through gas-phase oxonium and carbenium ions that are stabilized through interactions with deprotonated Brønsted sites and/or the solid oxide lattice. This interpretation provides a rigorous thermochemical foundation for detailed microkinetic analysis, which we employ to regress elementary interaction energies and kinetic parameters—moving the field toward a fundamental description of reactivity in acid-catalyzed upgrading of γ-valerolactone.

Original languageEnglish (US)
Pages (from-to)640-656
Number of pages17
JournalJournal of Catalysis
Volume344
DOIs
StatePublished - Dec 1 2016

Keywords

  • Biomass upgrading
  • Decarboxylation
  • Microkinetic modeling
  • Ring opening
  • Solid acids
  • γ-valerolactone

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

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