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Title: Photoelectrochemistry
Author: Fisher, F. S.
ISNI:       0000 0001 3466 2393
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 1978
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The purpose of this work was to assess the potential of the Ru(II)(bipy)3 complexes as photogalvanic systems, using the criteria obtained from the theory for an ideal photogalvanic solar cell developed by Albery and Archer. To this end two techniques were developed to measure the rate of the thermal back reaction between the high energy photoproducts Ru(III) and Fe(II) The thermal back reaction is a serious loss process in such a cell. The first technique, the Optical Rotating Disc Electrode, was improved by the design and construction of new apparatus. It allowed measurement of most of the important parameters of a photogalvanic cell and confirmed much of the theory for such a cell. The second technique, Flash Electrolysis, first used by Perone, was developed for use with a transparent disc electrode. Further investigations of the thermal back reaction were made using the Stopped Flow technique. The results of these experiments on Ru(IIl)(bipy)3 and its derivatives show that the reaction obeys the Marcus theory of electron transfer. However the activation parameters are dominated by "compensation effects" which, at the elevated temperatures of a practical photogalvanic cell (> 60°C) , reduce the differences between different derivatives. The very similar rates of reaction so produced are much too high for the development of an efficient photogalvanic cell. Ru(II) (bipy)3 systems thus provide a useful model for other possible photogalvanic systems buc cannot be of any practical use themselves.
Supervisor: Albery, John Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Photoelectrochemistry ; Photogalvanography