Analysis of heterogeneous oxygen exchange and fuel oxidation on the catalytic surface of perovskite membranes

Jongsup Hong, Patrick Kirchen, Ahmed F. Ghoniem

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

The catalytic kinetics of oxygen surface exchange and fuel oxidation for a perovskite membrane is investigated in terms of the thermodynamic state in the immediate vicinity of or on the membrane surface. Perovskite membranes have been shown to exhibit both oxygen perm-selectivity and catalytic activity for hydrocarbon conversion. A fundamental description of their catalytic surface reactions is needed. In this study, we infer the kinetic parameters for heterogeneous oxygen surface exchange and catalytic fuel conversion reactions, based on permeation rate measurements and a spatially resolved physical model that incorporates detailed chemical kinetics and transport in the gas-phase. The conservation equations for surface and bulk species are coupled with those of the gas-phase species through the species production rates from surface reactions. It is shown that oxygen surface exchange is limited by dissociative/associative adsorption/desorption of oxygen molecules onto/from the membrane surface. On the sweep side, while the catalytic conversion of methane to methyl radical governs the overall surface reactions at high temperature, carbon monoxide oxidation on the membrane surface is dominant at low temperature. Given the sweep side conditions considered in ITM reactor experiments, gas-phase reactions also play an important role, indicating the significance of investigating both homogeneous and heterogeneous chemistry and their coupling when examining the results. We show that the local thermodynamic state at the membrane surface should be considered when constructing and examining models of oxygen permeation and heterogeneous chemistry.

Original languageEnglish
Pages (from-to)96-106
Number of pages11
JournalJournal of Membrane Science
Volume445
DOIs
Publication statusPublished - 2013 Oct 15

Fingerprint

Perovskite
Ion exchange
Oxygen
membranes
Membranes
Oxidation
oxidation
oxygen
Surface reactions
Gases
surface reactions
Thermodynamics
vapor phases
Permeation
Conversion Disorder
Temperature
Methane
Carbon Monoxide
chemistry
Hydrocarbons

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Materials Science(all)
  • Biochemistry
  • Filtration and Separation

Cite this

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abstract = "The catalytic kinetics of oxygen surface exchange and fuel oxidation for a perovskite membrane is investigated in terms of the thermodynamic state in the immediate vicinity of or on the membrane surface. Perovskite membranes have been shown to exhibit both oxygen perm-selectivity and catalytic activity for hydrocarbon conversion. A fundamental description of their catalytic surface reactions is needed. In this study, we infer the kinetic parameters for heterogeneous oxygen surface exchange and catalytic fuel conversion reactions, based on permeation rate measurements and a spatially resolved physical model that incorporates detailed chemical kinetics and transport in the gas-phase. The conservation equations for surface and bulk species are coupled with those of the gas-phase species through the species production rates from surface reactions. It is shown that oxygen surface exchange is limited by dissociative/associative adsorption/desorption of oxygen molecules onto/from the membrane surface. On the sweep side, while the catalytic conversion of methane to methyl radical governs the overall surface reactions at high temperature, carbon monoxide oxidation on the membrane surface is dominant at low temperature. Given the sweep side conditions considered in ITM reactor experiments, gas-phase reactions also play an important role, indicating the significance of investigating both homogeneous and heterogeneous chemistry and their coupling when examining the results. We show that the local thermodynamic state at the membrane surface should be considered when constructing and examining models of oxygen permeation and heterogeneous chemistry.",
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Analysis of heterogeneous oxygen exchange and fuel oxidation on the catalytic surface of perovskite membranes. / Hong, Jongsup; Kirchen, Patrick; Ghoniem, Ahmed F.

In: Journal of Membrane Science, Vol. 445, 15.10.2013, p. 96-106.

Research output: Contribution to journalArticle

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