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X-ray absorption spectroscopy studies of electrochemical processes

Smila-Castro, Ornella (2012)
Ph.D. thesis, University of Birmingham.

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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.

Type of Work:Ph.D. thesis.
Supervisor(s):Rayment, Trevor
School/Faculty:Colleges (2008 onwards) > College of Engineering & Physical Sciences
Department:School of Chemistry
Subjects:QD Chemistry
QH301 Biology
T Technology (General)
Institution:University of Birmingham
ID Code:3766
This unpublished thesis/dissertation is copyright of the author and/or third parties. The intellectual property rights of the author or third parties in respect of this work are as defined by The Copyright Designs and Patents Act 1988 or as modified by any successor legislation. Any use made of information contained in this thesis/dissertation must be in accordance with that legislation and must be properly acknowledged. Further distribution or reproduction in any format is prohibited without the permission of the copyright holder.
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