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Oxygen non-stoichiometry profoundly impacts the electrical, magnetic, and catalytic properties of metal oxide. Limited by the low mass and volume of thin oxide films, conventional quantification methods, such as thermogravimetry, are not directly applicable. While chemical capacitance has been successfully applied to monitor oxygen non-stoichiometry in thin oxide films, detailed a-priori understanding of the defect chemistry is often very helpful in its interpretation. In this study, changes in non-stoichiometry in Pr doped CeO2 (PCO) thin films are measured by coulometric titration. I-V titration measurements are performed on electrochemical cells, over the temperature range from 550 to 700 ℃, oxygen partial pressure range from 10-4 to 0.21 atm, and bias range of -50 mV to 50 mV, to extract changes in stoichiometry. The results agree well with values obtained by chemical capacitance, demonstrating the utility in applying coulometric titration to investigate oxygen non-stoichiometry in oxide thin films.

Exsolution is a recent advancement for fabricating oxide-supported metal nanoparticle catalysts via phase precipitation out of a host oxide. A fundamental understanding and control of the exsolution kinetics are needed to engineer exsolved nanoparticles to obtain higher catalytic activity toward clean energy and fuel conversion. Since oxygen release via oxygen vacancy formation in the host oxide is behind oxide reduction and metal exsolution, we hypothesize that the kinetics of metal exsolution should depend on the kinetics of oxygen release, in addition to the kinetics of metal cation diffusion. Here, we probe the surface exsolution kinetics both experimentally and theoretically using thin-film perovskite SrTi0.65Fe0.35O3 (STF) as a model system. We quantitatively demonstrated that in this system the surface oxygen release governs the metal nanoparticle exsolution kinetics. As a result, by increasing the oxygen release rate in STF, either by reducing the sample thickness or by increasing the surface reactivity, one can effectively accelerate the Fe0 exsolution kinetics. Fast oxygen release kinetics in STF not only shortened the prereduction time prior to the exsolution onset, but also increased the total quantity of exsolved Fe0 over time, which agrees well with the predictions from our analytical kinetic modeling. The consistency between the results obtained from in situ experiments and analytical modeling provides a predictive capability for tailoring exsolution, and highlights the importance of engineering host oxide surface oxygen release kinetics in designing exsolved nanocatalysts.

In this review, we consider the detrimental effects of Si-contamination on electrochemical applications, broadly conceived, in which both ions and electrons play key roles in device operation and where exchange of oxygen between the gas and solid phase is likewise essential for operation.