Outstanding Properties and Performance of CaTi[subscript 0.5]Mn[subscript 0.5]O[subscript 3?delta] f
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Qian, Xin↗
Engineering topics
Yuan, Weizi
Publications and source records attributed to Yuan, Weizi.
Local Multimodal Electro-Chemical-Structural Characterization of Solid-Electrolyte Grain Boundaries
Typical models of polycrystalline ionic materials treat the grain boundary properties as single valued, without consideration of the full range of values that define the macroscopically measured average. Here a unique experimental platform suitable for local multimodal characterization of individual grain boundaries in bicrystal fibers is reported. A variation of three orders of magnitude in the grain boundary conductivity of ceria is observed, as measured across six individual bicrystals by both alternating current impedance spectroscopy and direct current (D.C.) linear sweep voltammetry. Nonlinear behavior of the D.C. measurements is consistent with resistance due to a space charge effect. Time-of-flight secondary ion beam spectroscopy reveals a correlation between grain boundary resistance and the concentration of impurities Si, Al, and Ca segregated at the grain boundaries, although the bulk concentrations of these impurities are negligible. Electron backscatter diffraction analysis of the crystal orientations suggests a correlation between the misorientation across the grain boundaries and grain boundary resistance. These correlations point towards a grain boundary resistance that arises from impurity-generated space charge effects and variations in impurity concentration and hence resistivity driven by the energetics of impurity segregation to grain boundaries of differing surface energies.
36 MATERIALS SCIENCE↗
Unexpected trends in the enhanced Ce 3+ surface concentration in ceria–zirconia catalyst materials
Despite the immense importance of ceria–zirconia solid solutions in heterogeneous catalysis, and the growing consensus that catalytic activity correlates with the concentration of reduced Ce 3+ species and accompanying oxygen vacancies, the extent of reduction at the surfaces of these materials, where catalysis occurs, is unknown. Using angle-resolved X-ray Absorption Near Edge Spectroscopy (XANES), we quantify under technologically relevant conditions the Ce 3+ concentration in the surface (2–3 nm) and bulk regions of ceria–zirconia films grown on single crystal yttria-stabilized zirconia, YSZ (001). In all circumstances, we observe substantial Ce 3+ enrichment at the surface relative to the bulk. Surprisingly, the degree of enhancement is highest in the absence of Zr. This behavior stands in direct contrast to that of the bulk in which the Ce 3+ concentration monotonically increases with increasing Zr content. Overall, these results suggest that while Zr enhances the oxygen storage capacity in ceria, undoped ceria may have higher surface catalytic activity. They further urge caution in the use of bulk properties as surrogate descriptors for surface characteristics and hence catalytic activity.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗