TY - JOUR
T1 - Bulk Properties of the Oxygen Reduction Catalyst SrCo0.9Nb0.1O3-δ
AU - Usiskin, Robert E.
AU - Davenport, Timothy C.
AU - Wang, Richard Y.
AU - Guan, Webster
AU - Haile, Sossina M.
N1 - Funding Information:
This work was funded by the National Science Foundation (Award No. DMR-0918224), the California Institute of Technology Summer Undergraduate Research Fellowship program (to R.W. and W.G.), and an EERE Postdoctoral Research Award (to T.C.D.). (Opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation.)
Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/5/10
Y1 - 2016/5/10
N2 - The perovskite SrCo0.9Nb0.1O3-δ (SCN) has excellent electrochemical activity toward oxygen reduction, and it is also valuable as a possible model material for other state-of-the-art perovskite catalysts based on strontium and cobalt, such as Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF). Here we report thermogravimetric, conductivity, and diffraction measurements from SCN. We find that the thermodynamic stability limits of SCN are slightly more favorable than those reported for BSCF, although both materials exhibit a slow oxidative partial decomposition under likely operating conditions. In SCN, this decomposition is thermodynamically preferred when the average formal oxidation state of cobalt is greater than ∼3.0+, but due to sluggish kinetics, metastable SCN with higher cobalt valence can be observed. The oxygen stoichiometry 3-δ varies from 2.45 to 2.70 under the conditions studied, 500-1000 °C and 10-4-1 bar O2, which encompass both stable and metastable behavior. The electronic conductivity is p-type and thermally activated, with a value at 600 °C in air of 250 S cm-1, comparable to that of La0.8Sr0.2MnO3-δ. The polaron migration enthalpy decreases linearly from 0.30 to 0.05 eV as 3-δ increases from 2.52 to 2.64. Thermal and chemical expansivities are also reported.
AB - The perovskite SrCo0.9Nb0.1O3-δ (SCN) has excellent electrochemical activity toward oxygen reduction, and it is also valuable as a possible model material for other state-of-the-art perovskite catalysts based on strontium and cobalt, such as Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF). Here we report thermogravimetric, conductivity, and diffraction measurements from SCN. We find that the thermodynamic stability limits of SCN are slightly more favorable than those reported for BSCF, although both materials exhibit a slow oxidative partial decomposition under likely operating conditions. In SCN, this decomposition is thermodynamically preferred when the average formal oxidation state of cobalt is greater than ∼3.0+, but due to sluggish kinetics, metastable SCN with higher cobalt valence can be observed. The oxygen stoichiometry 3-δ varies from 2.45 to 2.70 under the conditions studied, 500-1000 °C and 10-4-1 bar O2, which encompass both stable and metastable behavior. The electronic conductivity is p-type and thermally activated, with a value at 600 °C in air of 250 S cm-1, comparable to that of La0.8Sr0.2MnO3-δ. The polaron migration enthalpy decreases linearly from 0.30 to 0.05 eV as 3-δ increases from 2.52 to 2.64. Thermal and chemical expansivities are also reported.
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U2 - 10.1021/acs.chemmater.5b04783
DO - 10.1021/acs.chemmater.5b04783
M3 - Article
AN - SCOPUS:84969158075
SN - 0897-4756
VL - 28
SP - 2599
EP - 2608
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 8
ER -