Direct Observation of Oxygen Dissociation on Non-Stoichiometric Metal Oxide Catalysts

Huang, Yi-Lin; Pellegrinelli, Chistopher; Wachsman, Eric D.

doi:10.1002/anie.201607700

Direct Observation of Oxygen Dissociation on Non-Stoichiometric Metal Oxide Catalysts

Journal Article · Wed Nov 09 00:00:00 EST 2016 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201607700· OSTI ID:1533085

Huang, Yi-Lin ^[1]; Pellegrinelli, Chistopher ^[2]; Wachsman, Eric D. ^[2]

Univ. of Maryland, College Park, MD (United States). University of Maryland Energy Research Center; DOE/OSTI
Univ. of Maryland, College Park, MD (United States). University of Maryland Energy Research Center

Oxygen dissociation on metal oxides is a key reaction step, limiting the efficiency of numerous technologies. The complexity of the multi-step oxygen reduction reaction (ORR) makes it difficult to investigate the oxygen dissociation step independently. Direct observation of the oxygen dissociation process is described, quantitatively, on perovskites La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ and (La_0.8Sr_0.2)_0.95MnO_3±δ, using gas-phase isotope-exchange with a 1:1 ¹⁶O₂:¹⁸O₂ ratio. Oxygen transport mechanisms between gas–surface reactions and surface–bulk exchange are deconvoluted. Our findings show that regardless of participation of lattice oxygen, La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ is better at oxygen dissociation than (La_0.8Sr_0.2)_0.95MnO_3±δ. Heteroexchange, involving lattice oxygen, dominates on La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ. In contrast, (La_0.8Sr_0.2)_0.95MnO_3±δ shows both homoexchange and heteroexchange, with the latter only happening above 600 °C. Using a 1:1 isotope mixture, a simple method is presented for separation of the oxygen dissociation step from the overall ORR.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Maryland, College Park, MD (United States)

Sponsoring Organization:: USDOE Office of Fossil Energy (FE)

Grant/Contract Number:: FE0009084

OSTI ID:: 1533085

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 49 Vol. 55; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
heterogeneous catalysis
isotopes
non-stoichiometric compounds
oxygen dissociation
oxygen exchange

Direct Observation of Oxygen Dissociation on Non-Stoichiometric Metal Oxide Catalysts

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