Electrocatalytic and Fundamental Properties of Nanoscale Materials and Development of New Nanoscale Electrochemical Methods
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This dissertation mainly discusses the fundamental properties and electrocatalytic activity of single, isolated nanomaterial structures, such as nanowires, nanoparticles and graphene. It also discusses the development of new nanoscale electrochemical techniques to investigate various aspects of heterogeneous catalysis and single cell analysis. There is a brief introduction about the nature of electrochemistry and electrochemical catalysts as well as some various nanomaterials and voltammetric techniques involved in this work. The fabrication and of new ultralong metal nanowires made from platinum or gold through a laser assisted mechanical pulling procedure is discussed in chapter 2. Single platinum nanowires of this type are then used to study the Oxygen Reduction Reaction (ORR) on nanowires with various diameters in Chapter 3. The catalytic activities of several different nanoparticles are studied in Chapters 4 and 5 using the technique of Fast Scan Cyclic Voltammetry (FSCV), where detailed chemical information can be obtained from nanoparticle collision events by recording single nanoparticle Cyclic Voltammograms (CVs) for the oxidation of hydrazine. Combined with numerical simulations, the single nanoparticle CVs allow for the determination of the electron transfer kinetics and the Gibbs free energy of activation for hydrazine oxidation. These combined methods can be a powerful tool in many aspects of fundamental catalytic research. Chapter 6 details the phenomena of fast formation and growth of platinum oxide at low anodic potentials using platinum nanoelectrodes as model nanoparticle electrocatalysts. Chapter 7 discusses the technique of Fluorescence Enabled Electrochemical Microscopy (FEEM) and its application towards heterogeneous electrocatalyst screening, where a fluorogenic reaction is monitored at one side of an array of closed bipolar electrodes, which is coupled to a reaction occurring at the same region on the other side of the array. Chapter 8 is a study of the electrocatalytic activity of single graphene sheets with different numbers of layers for the ORR. The testing of recessed ring disk electrodes for the purpose of molecular scavenging during single cell exocytosis experiments is presented in Chapter 9 and chapter 10 describes the design and fabrication of two different Transmission Electron Microscopy (TEM) chip based electrodes for the goal of in-situ TEM experiments.
- Chemistry