Abstract
It is established by ESR that the adsorption of an NO + O2 mixture at 20°C on oxidized CeO2 (O2, T = 400–700°C) produces radical anions O −2 located both on isolated Ce4+ cations (O −2 (1)) and in associated anionic vacancies (O −2 (2)). These species differ in thermal stability. For example, O −2 (2) decomposes at 20°C, while O −2 (1) decomposes at 50°C. Only O −2 (1) species are observed at −196°C in ZrO2-supported CeO2. In the case of NO + O2 adsorption at 20°C, O −2 is stabilized on Zr4+ cations and decomposes at 270°C. Increasing the cerium oxide content of the ZrO2 surface from 0.5 to 10% only partially inhibits the formation of O −2 -Zr4+. The Zr4+ cation is shown to possess a higher Lewis acidity than the Ce4+ cation, and the ionic bond in O −2 -Zr4+ complexes is stronger than that in O −2 -Ce4+ complexes. ESR, temperature-programmed desorption, and IR spectroscopic data for various adsorption complexes of NO on CeO2 suggest that, in the key step of O −2 formation, free electrons appear on the surface owing to the conversion of adsorbed NO molecules into nitrito chelates on coordinately unsaturated ion pairs Ce4+-O −2 .
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Translated from Kinetika i Kataliz, Vol. 46, No. 3, 2005, pp. 414–422.
Original Russian Text Copyright © 2005 by Il’ichev, Shibanova, Ukharskii, Kuli-zade, Korchak.
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Il’ichev, A.N., Shibanova, M.D., Ukharskii, A.A. et al. Mechanism of the Formation of O −2 Radical Anions on CeO2 and (0.5–10)%CeO2/ZrO2 during the Adsorption of an NO-O2 Mixture. Kinet Catal 46, 387–395 (2005). https://doi.org/10.1007/s10975-005-0090-z
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DOI: https://doi.org/10.1007/s10975-005-0090-z