Energy conversion and storage via photoelectrochemical methods

Altalhi, Amal A.

Chemistry
2013

Thesis or dissertation


Rights
© 2013 Amal A Altalhi. All rights reserved. No part of this publication may be reproduced without the written permission of the copyright holder.
Abstract

Photoelectro analytical chemistry provides an elegant technique by which to explore, amongst others, various industrial and environmental applications. To this end, four areas of photoelectroanalytical chemistry are investigated in order to develop industrially - and environmentally - relevant galvanic and photogalvanic cells, together with exploring the electro-generation of an industrially important molecule and diffusion factors they may affect this generation.

The first study is investigated a long-range charge transfer, using tert-butylferrocene (tBuFc) as model hydrophobic system. It is found that the apparent one-dimensional diffusion coefficient depends on the tBuFc loading. It is suggested that an efficient relay mechanism for electron transfer is through the partitioning of the oxidised form between the two subphases, with inter-pseudophase reaction.

However, the second study investigated the normal lyotropic liquid crystals (in the lamellar or hexagonal phases) as a route to afford a structured, three-dimensional, quasi-biphasic framework within which electron transfer cascades may take place using cyclic voltammetry. It is shown that these can take place through reagent partitioning between the hydrophobic and hydrophilic subphases, and it is illustrated how the structure and its orientation, the nature of the ionic doping of the framework, and the hydrophobicity of the redox analyte may give rise to changes in the observed voltammetric waveshape.

For the case of an artitifical mimic of the first few stages of Photosystem I, it is demonstrated that photo-induced electron transfer is likewise affected by the orientation, and develop a system of photon efficiency of ~0.1%.

Thirdly, a novel attempt at power production was attempted with the construction and optimisation of a photogalvanic cell system. A literature review was conducted and a system proposed utilizing 10-methylphenothiazine (NMP) as a light harvester and zinc as a sacrificial electrode with tetrabutylammonium chloride (TBAP) as a supporting electrolyte and chloroform as a mediator. The study aimed to create a cell that could be produced using industrial run-off or other waste water supplies.

A series of cells was produced with varying concentrations of both zinc and NMP solutions and the power conversions studied by producing a voltage-current plot for each system. A system that exhibited 9.02% conversion efficiency keep, future studies were conducted to show whether the zinc species effected the power conversion or if silver would act in a similar way.

A mechanism was proposed for the power production process and so studies using 2, 4-Dichlorophenol (DCP) rather than chloroform we conducted; it was believed that the dissociation step for DCP was step wise rather than concerted. Lower power production was seen in these cells as predicted by the reaction mechanism. Tris - (4-bromophenyl) - amine (TBA), an alternative light harvester to NMP, was used to see if altering the active chemical agent resulted in efficiency change.

Finally , A photogalvanic cell that employs 2,4-dichlorophenol as a fuel source, an N-substituted phenothiazine as light harvester, and sacrificial zinc anode is presented, and shown to afford a ca. 4% light-to-electrical power conversion efficiency in violet light.

Publisher
Department of Chemistry, The University of Hull
Supervisor
Wadhawan, Jay
Sponsor (Organisation)
Saudi Arabia. Wizārat al-Taʻlīm al-ʻĀlī
Qualification level
Doctoral
Qualification name
PhD
Language
English
Extent
3 MB
Identifier
hull:16512
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