In most applications, electrocatalysts exhibit a large surface area to volume ratio, for example using nanoparticles. To fully understand fundamental electrochemical processes at the length scale... Show moreIn most applications, electrocatalysts exhibit a large surface area to volume ratio, for example using nanoparticles. To fully understand fundamental electrochemical processes at the length scale of these nanoparticles, it is necessary to use specialized experimental techniques. In this thesis, the stability and activity of platinum electrode surfaces are studied at the nano- and micrometer scale using Electrochemical Scanning Probe Microscopy (EC-SPM) techniques. Chapters 2 and 3 describe the roughening of an atomically flat Pt(111) surface upon repetitive oxidation and reduction. These data were acquired using a combination of Electrochemical Scanning Tunneling Microscopy (EC-STM) and Cyclic Voltammetry (CV). Chapter 4 describes the development of a new technique to resolve small differences in local reactivity: voltammetric Scanning Electrochemical Cell Microscopy (SECCM). The power of this technique is demonstrated by studying the reactivity of a polycrystalline Pt sample towards hydrazine oxidation. Finally, Chapter 5 compares the reactivity of small Pt ultramicroelectrodes to that of conventional macroelectrodes. Show less
This thesis describes the construction of a second generation high-pressure, high-temperature scanning tunneling microscope, the ReactorSTM, with which the surfaces of catalysts can be studied... Show moreThis thesis describes the construction of a second generation high-pressure, high-temperature scanning tunneling microscope, the ReactorSTM, with which the surfaces of catalysts can be studied under relevant reaction conditions. Furthermore, the thesis describes three separate catalytic systems at ~ 1 bar, and elevated temperatures. Firstly, NO reduction on Pt(100), in which a mathematical model for the reaction mechanism, following Langmuir-Hinshelwood kinetics, is proposed. Secondly, CO oxidation, in which the Pt(110) surface is atomically resolved at high p, T. Thirdly, the thesis describes a successful pilot experiment about the hydrodesulphurization of thiophene, which is catalytically activated by molybdenum disulphide nano-crystallites on an Au(111) support. Show less