Microkinetic analysis of acetone hydrogenation over Pt/SiO 2

Xin Gao, Andreas Heyden, Omar A. Abdelrahman, Jesse Quentin Bond

Research output: Contribution to journalArticle

Abstract

The kinetics of vapor-phase acetone hydrogenation were investigated over a Pt/SiO 2 catalyst through a range of temperatures (303–435 K) and reactant partial pressures (p ACE = 0.3–140 Torr, p H2 = 100–930 Torr). We compile macroscopically observable reaction orders, apparent barriers, kinetic isotope effects, and reaction rates; and we present a microkinetic analysis that considers multiple rate control scenarios in two Horuiti-Polanyi-type mechanisms. Overall, our data are best described by a two-site model wherein atomic hydrogen adsorbs at a distinct set of active sites from organic species. We further propose that two surface reactions each exert partial rate control, and we illustrate that degree of rate control is sensitive to reaction conditions. Shifts in rate control are attributed primarily to changing surface coverage regimes, which highlights the significance of both free energies of activation and chemical-potential driving forces in dictating the kinetic significance of elementary steps. Despite our conclusion that surface reactions involving H-X bond formation are likely rate controlling, we observe that H 2 /D 2 switching minimally perturbs acetone hydrogenation rates. We interpret this by considering that observed kinetic isotope effects reflect a convolution of kinetic and thermodynamic impacts, which can obscure the elementary effects of changes in isotopic mass.

Original languageEnglish (US)
Pages (from-to)183-198
Number of pages16
JournalJournal of Catalysis
Volume374
DOIs
StatePublished - Jun 1 2019

Fingerprint

Acetone
acetone
Hydrogenation
hydrogenation
Kinetics
kinetics
Surface reactions
Isotopes
isotope effect
surface reactions
Chemical potential
Convolution
Partial pressure
Free energy
Reaction rates
Hydrogen
convolution integrals
Chemical activation
Vapors
partial pressure

Keywords

  • Acetone hydrogenation
  • Horiuti-Polanyi
  • Ketone hydrogenation
  • Kinetics
  • Microkinetic modelling
  • Platinum
  • Silica

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

Cite this

Microkinetic analysis of acetone hydrogenation over Pt/SiO 2 . / Gao, Xin; Heyden, Andreas; Abdelrahman, Omar A.; Bond, Jesse Quentin.

In: Journal of Catalysis, Vol. 374, 01.06.2019, p. 183-198.

Research output: Contribution to journalArticle

Gao, Xin ; Heyden, Andreas ; Abdelrahman, Omar A. ; Bond, Jesse Quentin. / Microkinetic analysis of acetone hydrogenation over Pt/SiO 2 In: Journal of Catalysis. 2019 ; Vol. 374. pp. 183-198.
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