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Memory effect of ZrO2 matrix on surface Co3O4–CoO transition

Published online by Cambridge University Press:  03 March 2011

H.C. Zeng ,
J. Lin  and
K.L. Tan
H.C. Zeng*
Affiliation:
Department of Chemical Engineering, Faculty of Engineering, National University of Singapore, 10 Kent Ridge Crescent, Singapore 0511
J. Lin
Affiliation:
Department of Physics, Faculty of Science, National University of Singapore, 10 Kent Ridge Crescent, Singapore 0511
K.L. Tan
Affiliation:
Department of Physics, Faculty of Science, National University of Singapore, 10 Kent Ridge Crescent, Singapore 0511
*
a)Author to whom correspondence should be addressed.
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Abstract

Cobalt oxide system Co3O4-CoO has been studied on the ZrO2 matrix surfaces with FTIR and XPS. The tetragonal and monoclinic ZrO2 matrix materials have been synthesized from the Zr-n-propoxide-acetylacetone-water-isopropanol system. The study shows that the ZrO2 matrix is able to retain the relative Co3O4:CoO population at elevated temperatures. The thermodynamically stable oxide population (Co3O4:CoO) at room temperature for ZrO2-supported Co3O4-CoO is about 50:50 (Co2+ :Co3+ = 2:1), which is markedly different from the 100:0 case (Co2+ :Co3+ = 1:2) for an unsupported Co3O4-CoO surface oxide system. The relative Co3O4 :CoO ratio in the surface region of the ZrO2 is temperature dependent but matrix-polymorph independent. The composition of an oxide solid solution formed by the Co3O4-CoO and matrices of ZrO2 is determined to have a cobalt molar percentage of 4.5%. Diffusion thermodynamic quantities are investigated, and the measured diffusion activation energy for a cobalt ion in the ZrO2 matrices is 0.21 eV. The mechanism of the ZrO2 memory effect on surface Co3O4-CoO transition will also be addressed.

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Articles
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Journal of Materials Research , Volume 10 , Issue 12 , December 1995 , pp. 3096 - 3105
Copyright
Copyright © Materials Research Society 1995

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