Electrosynthesis and Characterization of Main Group and Transition Metal Oxides

Chapter 1: General Introduction A brief review of solid state synthetic techniques is given. The research discussed in this thesis is introduced. Chapter 2: Electrosynthesis of Highly Oxidized Transition Metal and Main Group Oxides in Molten Hydroxides The development of electrosynthesis in molten hydroxides of oxides containing high valent transition metals and main group metals is described. Electrosynthesis is shown to be a viable route to such materials, including, KBiO 3, NaNiO2, NaxCoO2, Srl.75CuO5.13, NaBa2Cu3O5, Ca4PtO6, and Sr3NiPtO6. Experimental are discussed. The ionic conductivity of KBiO3 was determined to be 10-5 S/cm at 300 °C, about 3 orders of magnitude lower than the conducitivity of the analogous NaSbO3o 1/6NaF. The low conductivity of KBiO 3 was explained by the high size ratio of K+ to BiS+ compared to Na+ and Sb 5+, the low mobility of K+ compared to that of Na+, and the role of the K+ ion in stalilizing the Bi-O framework structure. Chapter 3: Structural and Magnetic Characterization of the One-Dimensional Oxides, Sr3MPtO 6, M = Co, Ni, Cu, Zn The synthesis and characterization of a family of one-dimensional oxides, Sr3MPtO6, M = Co, Ni, Cu, Zn, is described. The structure was determined using Rietveld analysis of powder X-ray and neutron diffraction data. Sr3MPtO6 contains infinite chains composed of alternating, face-sharing PtO6 octahedra and M06 trigonal prisms. Sr3ZnPtO6 is diamagnetic. Sr3CuPtO6 displays well-behaved linear chain Heisenberg antiferromagnetism, with IJI/k = 26.1 K and g = 2.21. Sr3NiPtO6, a S = 1 system, shows an onset of low-dimensional antiferromagnetism at -25 K, with no long-