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The electrochemical oxidation behaviors of the surfaces of platinum nanoparticles, one of the key phenomena in fuel cell developments, were investigated in situ and in real time, via time-resolved hard X-ray diffraction and energy dispersive X-ray absorption spectroscopy. Combining two complementary structural analyses, dynamical and inhomogenous structural changes occurring at the surfaces of nanoparticles were monitored on an atomic level with a time resolution of less than 1 s. After oxidation at 1.4 V vs RHE (reversible hydrogen electrode) in a 0.5 M H(2)SO(4) solution, longer Pt-O bonds (2.2-2.3 A that can be assigned to OHH and/or OH species) were first formed on the surface through the partial oxidation of water molecules. Next, these species turned to shorter Pt-O bonds (2.0 A, adsorbed atomic oxygen), and atomic oxygen was incorporated into the inner part of the nanoparticles, forming an initial monolayer oxide that had alpha-PtO(2)-like local structures with expanded Pt-Pt bonds (3.1 A). Finally, quasi-three-dimensional oxides with longer Pt-(O)-Pt bonds (3.5 A, precursor for beta-PtO(2)) grew on the surface, at almost 100 s after oxidation. Despite the very complex oxidation mechanism on the atomic level, XANES analysis indicated that the charge transfer from platinum to the adsorbed oxygen species was almost constant and rather small, that is, about 0.5 electrons per oxygen, up to two monolayers of oxygen. This means that ionic polarization hardly develops at this stage of the surface platinum's "oxide" growth.

Crystal structures of ferroelectric materials of stoichiometric SrBi2Ta2O9 (TC=300 °C) and Sr-deficient-and-Bi-excess Sr0.8Bi2.2Ta2O9 (TC=400 °C) were refined by neutron powder diffraction. Bi2O2 layer and TaO6 octahedra are considerably distorted and atomic displacements along the a axis cause ferroelectric spontaneous polarization. In Sr0.8Bi2.2Ta2O9, both Bi substitution and cation vacancies at the Sr site were revealed and a chemical composition of (Sr0.82Bi0.12)Bi2Ta2O9.0 was obtained. The calculated polarization of Sr0.8Bi2.2Ta2O9 is larger than that of the stoichiometric sample, which is consistent with observations of remanent polarization in thin-film capacitors. The Bi substitution and the cation vacancies at the Sr site enhance structural distortion in the TaO6 octahedra and lead to the larger ferroelectric spontaneous polarization and the higher Curie temperature.

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