Electrochemical synthesis and characterization of redox-active electrode materials

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Hahn, Benjamin Phillip

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This dissertation explores cathodic electrodeposition mechanisms that describe the synthesis of redox-active electrode materials. Several interesting elements are known to deposit at negative potentials (e.g., Mo, Re, Se), and by extending this work, we can tailor the growth of new binary systems (e.g., MoxRe₁₋xOy, MoxSe₁₋xOy) that have enhanced optical and electronic properties. To grasp the subtleties of deposition and understand how the growth of a particular phase is influenced by other species in solution, several analytical methodologies are used to thoroughly characterize film deposition, including chronocoulometry, voltammetry, nanogravimetry, UV-Visible spectroelectrochemistry, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and inductively coupled plasma mass spectrometry (ICPMS). Chapter 1 is a general introduction that discusses the growth of redox-active metal oxides and alloys with an emphasis on tuning the composition to enhance material performance. Chapter 2 proposes a mechanistic pathway for the deposition of rhenium films from an acidic perrhenate (ReVIIO₄⁻) solution containing both metallic and oxide components. Unlike many other metal anions, it was observed that ReVIIO₄⁻ adsorbs to the electrode surface prior to reduction. As such, ReVIIO₄⁻ is ideally situated to be a redox-active mediator for other electrochemical reactions, and in Chapter 3, this dissertation explores how ReVIIO₄⁻ increases the deposition efficiency of Mo oxide deposition. Depth profiling XPS supported by electrochemical studies demonstrated that Mo and Re deposit separately to form an inhomogeneous material, MoxRe₁₋xOy (0.6 < x ≤ 1.0). Over a limited potential range from –0.3 V to –0.7 V (vs Ag/AgCl) the rhenium mole fraction increases linearly with the applied voltage. Chapter 4 explores the deposition of MoxSe₁₋xOy, and in this case, the incorporation of Mo species in solution shifts the deposition of Se⁰ to more positive potentials. Depending on the applied potential used, voltammetry experiments suggest that a small amount of Mo (<5%) reduces to the zero-valent phase to yield the photosensitive alloy, MoxSey. Chapter 5 discusses future work and presents preliminary data describing the deposition of Se⁰ on ITO using adsorbed ReVIIO₄⁻ as a redox mediator.




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