Metal Oxides as Electrocatalysts at Oxygen Electrodes in Electrochemical Systems

Fuel cells, one of the most widely studied electrochemical energy conversion devices, together with electrolyzers, a promising energy storage system for natural renewable energy and source of purified hydrogen, have attracted significant research attention in recent years as the demand for energy continues to increase with no end to this energy expansion in sight. However, electrochemical reactions occurring at oxygen electrodes such as the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) have very slow kinetics, which has limited the industrialization of both fuel cells and electrolyzers because slow kinetics leads directly high reaction overpotentials. Metal oxides have been widely adopted in terms of electrocatalysts for these oxygen reactions, either as as a support to enhance the stability or activity of platinum, or as the direct catalysts for ORR and OER in alkaline media. However, what is not known is how and why metal oxides as support materials can influence the performance of precious metals through their interactions, what the active sites are for different electrochemical reactions and how to control the desired phases by manipulating the synthesis conditions. This study will probe these very important questions. Chapter 1 of this work provides a background into the ORR/OER mechanism, active sites, and catalyst candidates in electrochemical devices. Chapter 2 presents experimental approaches including material synthesis, and both physical and II electrochemical characterization. Chapters 3 and 4 of this study investigate doped metal carbides and metal oxides as support materials for platinum and iridium catalysts for the ORR and OER, respectively, in acidic electrolytes. The Chapter 3 is an investigation of tungsten carbide modified with titanium as a potential non-carbon support for platinum during the ORR in acid media. Chapter 4 discusses the relationship between the synthesis parameters of iridium/iridium oxide supported on titanium-doped tungsten oxide and its durability both ex-situ in a three-electrode cell on a rotating disk electrode (RDE) and in-situ in an operating electrolyzer. Chapter 5 discusses a new method to determine the electrochemically active area of iridium oxide, one of the most common anode catalysts in commercial PEM electrolyzers, in-situ through its electrochemical psuedocapacitance. Chapter 6 probes the performance and function of tin-doped indium oxides (ITO) as a support for platinum ORR catalyst in alkaline media. Metal-support interactions were studied mainly through X-ray photoelectron spectroscopy and electrochemical measurements. Chapter 7 focuses on the electrocatalysis of carbon nanotube (CNT)-supported cobalt oxide for both oxygen reduction and evolution reactions in alkaline media. An optimized procedure to produce a highly stable and active bifunctional ORR/OER hybrid catalyst was developed along with an understanding of the impact of metal oxide anchoring sites and synthesis parameters on catalyst durability. This part of the study provides novel perspectives for the design of carbon-based, hybrid materials and insight into the synthesis-property relationships for these and future electrocatalysts. In summary, this work has studied metal oxides as catalysts and support materials for precious metals during aqueous oxygen reactions. Wherever possible, the III fundamental cause for their behavior, including enhanced electrocatalytic activity and durability, was probed thoroughly through physical and electrochemical characterizatio