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- W2041941252 abstract "Abstract The fluorite oxides ceria and urania can be made non-stoichiometric by loss and gain, respectively, of oxygen atoms, thereby forming CeO2−x and UO2+x. The former now contains Ce3+ and Ce4+ ions and both single crystal and powder forms are blue and exhibit electron transfer in the form of intervalence spectra. The absorption spectra of pure and reduced ceria crystals are interpreted and used to help resolve electrical conductivity studies. Solid solutions of ceria and urania are blue-black and here electron transfer is of the form Ce(IV)+U(IV)→Ce(III)+U(V). The intervalence contribution to the absorption spectrum of ultra-thin single crystal wafers of UO2+x is only available as a difference spectrum, using the UO2 spectrum as reference. The U5+ ions formed and contributing to the intervalence spectra in freshly oxidised samples, quenched from UO2+x at high temperature, were found to be metastable at ambient temperature and slowly oxidised to U6+. The intervalence spectral profile changed significantly and slowly with time. Thus in aged crystals the electron transfer in the intervalence spectrum is principally due to U(IV)+U(VI)→U(V)+U(V). Monitoring these changes should yield information on the precipitation of interstitial clusters containing oxygen out of the urania matrix into aggregates and hence the growth as U3O7 on surfaces and at grain boundaries." @default.
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- W2041941252 date "1994-10-01" @default.
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- W2041941252 title "Electron transfer reactions in non-stoichiometric ceria and urania" @default.
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- W2041941252 doi "https://doi.org/10.1016/0020-1693(94)04062-1" @default.
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