We report the use of X-ray pair distribution function (PDF) to study the structure of a ruthenium oxide nanoskin that has been synthesized as a glassy film supported upon a silicon oxide fiber paper backbone (RuOx@SiO2). We have previously described this non–line–of–sight deposition via a liquid-phase process to generate a single–unit–layer thick film of RuOx. The atypical use of an aqueous solution of ruthenium tetraoxide (RuO4) synthesizes an unusual corundum-like ruthenium oxide that exists in sun-nano particulate form. The solution-phase synthetic protocol allows deposition of thin, solid films on a variety of substrates including 3D carbon nanofoams, silica fibers, and flat surfaces. Deposition of ruthenium oxide on flat pieces of sodium chloride allows the film to be removed for creation of ‘free-standing’ ruthenium oxide films for layering on other materials. Structurally, differential PDFs show correlations of the RuOx that do not correspond to rutile or hydrous RuO2·xH2O structures. Previous examinations established that a corundum phase of ruthenium oxide, Ru2O3, would be unstable relative to the rutile phase, RuO2 and quickly disproportionate; however, the PDF experiments show that the local structure of the ruthenia in RuOx@SiO2 can be modeled as a sub-nano-particulate corundum structure. This is particularly unusual as corundum ruthenia has never been previously examined, but is consistent with studies that have shown the surface of ruthenium oxide to be oxide-deficient. Alternatively, the PDF results may be explained by correlations of the ruthenium oxide with the silicon oxide backbone. We explore the local structure of the RuOx phase to explore how solution deposition processes can create new materials.

Structure of ruthenium oxide thin films synthesized via decomposition of a common staining agent

250th National Meeting (2015)

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