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Issue 43, 2011
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Direct evidence of redox interaction between metal ion and support oxide in Ce0.98Pd0.02O2−δ by a combined electrochemical and XPS study

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Abstract

A combined electrochemical method and X-ray photo electron spectroscopy (XPS) has been utilized to understand the Pd2+/CeO2 interaction in Ce1−xPdxO2−δ (x = 0.02). A constant positive potential (chronoamperometry) is applied to Ce0.98Pd0.02O2−δ working electrode which causes Ce4+ to reduce to Ce3+ to the extent of ∼35%, while Pd remains in the +2 oxidation state. Electrochemically cycling this electrode between 0.0–1.2 V reverts back to the original state of the catalyst. This reversibility is attributed to the reversible reduction of Ce4+ to Ce3+ state. CeO2 electrode with no metal component reduces to CeO2−y (y ∼ 0.4) after applying 1.2 V which is not reversible and the original composition of CeO2 cannot be brought back in any electrochemical condition. During the electro-catalytic oxygen evolution reaction at a constant 1.2 V for 1000 s, Ce0.98Pd0.02O2−δ reaches a steady state composition with Pd in the +2 states and Ce4+ : Ce3+ in the ratio of 0.65 : 0.35. This composition can be denoted as Ce4+0.63Ce3+0.35Pd0.02O2−δy (y∼0.17). When pure CeO2 is put under similar electrochemical condition, it never reaches the steady state composition and reduces almost to 85%. Thus, Ce0.98Pd0.02O2−δ forms a stable electrode for the electro-oxidation of H2O to O2 unlike CeO2 due to the metal support interaction.

Graphical abstract: Direct evidence of redox interaction between metal ion and support oxide in Ce0.98Pd0.02O2−δ by a combined electrochemical and XPS study

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Publication details

The article was received on 01 Jul 2011, accepted on 19 Aug 2011 and first published on 26 Sep 2011


Article type: Paper
DOI: 10.1039/C1DT11262G
Dalton Trans., 2011,40, 11480-11489

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    Direct evidence of redox interaction between metal ion and support oxide in Ce0.98Pd0.02O2−δ by a combined electrochemical and XPS study

    S. Sharma, B. D. Mukri and M. S. Hegde, Dalton Trans., 2011, 40, 11480
    DOI: 10.1039/C1DT11262G

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