Graduate Thesis Or Dissertation
 

Investigation of the structural influence on the properties of functional inorganic oxides

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  • While properties are extremely important from an application point of view, it is crucial to have a detailed understanding of the underlying structural influence. Once a concrete correlation between the structure and the observed property is established, rational design of novel materials with optimized properties can be realized. These optimized materials lead to advancements in technology in a variety of applications, including new building materials, faster electronic devices, and more efficient catalysts. This dissertation examines the structural influence on the observed properties in a series of metal oxide materials for electronic and energy applications. A series of pyrochlores Ag[subscript 1-nx]M[superscript n][subscript x]SbO₃ (M = Na⁺, K⁺, Tl⁺, and Cd²⁺) has been studied to evaluate the structural influence on the samples' photocatalytic activity. A complete solid solution between the anion-deficient pyrochlore Ag₂Sb₂O₆ and the ideal pyrochlore Cd₂Sb₂O₇ has been synthesized through the standard solid state ceramic method. Each composition has been characterized by various different techniques, including powder X-ray diffraction, optical spectroscopy, electron paramagnetic resonance and ¹²¹Sb Mössbauer spectroscopy. Computational methods based on density functional theory complement this investigation. Photocatalytic activity has been studied, and transport properties have been measured on pellets densified by spark plasma sintering. The analysis of the data collected from these various techniques enables a comprehensive characterization of the complete solid solution and revealed an anomalous behavior in the Cd-rich end of the solid solution, which has been proposed to arise from a possible radical O⁻ species in small concentrations. Polycrystalline samples of the pyrochlore series Ag[subscript 1-nx]M[superscript n][subscript x]SbO₃ (M = Na⁺, K⁺ and Tl[superscript +/3+]) have been structurally analyzed through total scattering techniques and evaluated for photocatalytic activity. The upper limits of x obtained are 0.08 for Na, 0.16 for K, and 0.17 for Tl. The Ag⁺ cation occupies a site with inversion symmetry on a 3-fold axis. When the smaller Na⁺ cation substitutes for Ag⁺, it is displaced by about 0.6 Å perpendicular to the 3-fold axis to achieve shorter Na-O bond distances. When the larger Tl⁺ cation substitutes for Ag⁺, it is displaced by about 1.14 Å along the 3-fold axis and achieves an environment typical of a lone pair cation. Some of the Tl³⁺ from the precursor remains unreduced, leading to a formula of Ag₀.₇₇Tl⁺₀.₁₃Tl³⁺₀.₀₄SbO₃.₀₄. The position of the K⁺ dopant was effectively modeled assuming that K⁺ occupied the same site as Ag⁺. The expansion of the lattice caused by substitution of the larger K⁺ and Tl⁺ cations results in longer Ag-O bond lengths, which would reduce the overlap of the Ag 4d and O 2p orbitals that compose the valence band maximum. Substitution of the smaller Na⁺ results in a decrease in the Ag-O bond distance, thus increasing the overlap of the Ag 4d and O 2p orbitals. An increase in the photocatalytic activity has been observed for the nominal composition Ag₀.₈Na₀.₂SbO₃ made through solid state synthesis, and this is attributed to both the slight decrease in the band gap and the increase in pore dimensions compared to the parent compound AgSbO₃. The structural transitions in Cd₂Nb₂O[subscript 7-x]S[subscript x] (x = 0, 0.25, 0.5, and 0.7) have been studied to determine the origin of ferroelectricity in pyrochlore oxides. For x = 0, 0.25, and 0.5 peak splitting indicative of a transition to orthorhombic symmetry is observed below the transition temperature. In the x = 0.7 sample, the evolution of new peaks suggest a cubic space group is retained below the phase transition accompanied by a loss of the face-centering symmetry. The observed lowering of symmetry may be responsible for the transition into a ferroelectric phase, and may be driven by a strong displacement of both the Nb and Cd from the high- to low-symmetry structures. The S content may drive the stability if different ferroelectric phases, as no trend was observed with increasing content in the ferroelectric Curie temperatures of the samples. The structure of the hollandites A[subscript x]Ru₄O₈ (A = K⁺, Rb⁺) has been studied through total scattering techniques upon cation exchange with Na⁺ on the A-site to evaluate the effect on the quasi-one dimensional (Q1D) nature of these materials. It is observed that the A-site of the hollandite structure is not fully occupied when A = K⁺, Rb⁺, and full A-site occupancy is achieved after ion exchange with NaNO₃. All samples exhibit Pauli paramagnetism, and this is primarily due to a large low temperature range of metallic conduction. The double chains of edge-shared RuO₆ octahedra and corner shared double chains found in the channel of the hollandite structure promotes two conduction mechanisms: ρ∥ (intra-chain metallic) and ρ⊥ (inter-chain hopping). The coexistence of ρ∥ and ρ⊥ gives rise to metallic conductivity below T[subscript max] (suppressed hopping at lower temperature) and semiconductivity above T[subscript max] (intra-chain mean free path becomes smaller than the inter-chain hopping distance), exhibiting the Q1D conduction at lower temperatures. The inter-chain distance is larger in the Rb-containing samples, and consequently the region dominated by intra-chain metallic conduction increases, along with an increase in T[subscript max].
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