How temperature influences the stoichiometry of CeTi2O6

Of the many materials examined for the sequestration of nuclear waste, Ti oxides have received considerable attention. Brannerite (UTi2O6), in particular, has been studied extensively for this application. The Ce analogue of this material (CeTi2O6) has been widely investigated instead of the actinide versions owing to the reduced safety hazards and because Ce has similar crystal chemistry to U and Pu. In this study, examination of Ti K-, Ce L3-, and Ce M4,5-edge XANES spectra lead to the conclusion that CeTi2O6 was O-deficient when synthesized at high temperature and then quench cooled, and that the degree of O-deficiency was reduced upon post-annealing at lower temperatures. These observations can be ascribed to a temperature-dependant Ce3+/Ce4+ redox couple. This investigation suggests that Ce-containing materials may not properly simulate the actinide-bearing analogues; however, CeTi2O6 could be useful for other applications, such as catalysis.

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► CeTi2O6 is O-deficient when synthesized at high temperature.
► The O-deficiency of CeTi2O6 can vary because of the Ce3+/Ce4+ redox couple.
►  Ce may not always be an appropriate simulator element for U.