X-ray absorption spectroscopy studies of electrochemical processes

Electron transfer is a key part of many chemical, biological and physical processes, that is commonly studied by electrochemical methods, which give insight into reaction mechanisms but no structural information. It is necessary to combine electroanalysis with another technique to gain essential knowledge of metal-ligand bond length and oxidation states. X-ray absorption spectroscopy (XAS) can provide these data for species in dilute solution and, if combined with electrochemistry, could potentially provide powerful insight into electron transfer reactions. This dissertation describes the development and application of techniques for the study of electrochemical intermediates by XAS. Chapters 2 and 3 introduce the theory and practice of electrochemistry and spectroscopy with emphasis on XAS. Chapter 4 describes the development of variable-temperature spectroelectrolysis cells for the study of electrochemical intermediates. In Chapter 5, the electrochemical behaviour of Cp\( \ast \)Rh(CO)\(_2\), is investigated as an organometallic compound representative of the redox chemistry studied in this thesis. Chapter 6 describes a new approach to the study of electrochemical intermediates in which a miniature electrolysis cell is combined with a microdispenser so that electrochemical intermediates can be generated and then dispensed, quenched at low temperature prior to study by XAS. Chapter 7 contains final conclusions.EThOS - Electronic Theses Online ServiceGBUnited Kingdo