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Reference: Dare-Edwards, M. P., (1981). Mechanistic studies on semiconductor electrodes. DPhil. University of Oxford.Citable link to this page:


Mechanistic studies on semiconductor electrodes

Abstract: A study has been undertaken of the detailed photoelectrochemistry ofa number of III-V and oxide semiconductors. In particular, the work hasbeen aimed at obtaining a material which can act as a stable and efficientphotoelectrode for the solar photoelectrolysis of water. However to achievethis aim, it was considered essential to obtain a far deeper understandingof the mechanisms of the electrochemical reactions taking place at thesemiconductor/electrolyte interface.The mechanism for Hydrogen evolution from the surfaces of the p-typeIII-V materials has represented a particular problem. P-type GaP was chosenas the representative member of the III-V materials and a mechanistic studyhas been made of the material using a.c. and d.c. experiments in additionto a detailed interfacial impedance analysis. A model for the Hydrogenevolution reaction has been proposed invoking surface bound Hydrogen atomsas both intermediates in the desired reaction and also as photogeneratedsurface states in parasitic recombination reactions. With the experienceof the work on p-GaP, the analagous mechanisms to those found on p-GaP havebeen found to be consistent with results obtained on p-GaAs, p-InP andp-GaSb. However for these latter materials, additional complexities havearisen from their greater instability with respect to cathodic corrosion.A method has been sought for modifying the surface of the III-Vmaterials in order to obtain improved Hydrogen evolution efficiencies. Sucha modification has been discovered for p-GaP by the adsorption of a Rutheniumspecies from solutions of crude RuC13.xH20. Its mode of operation is discussedat length.For the oxide materials, a semiconducting oxide has been sought thatpossesses the ideal band energies and bandgap to obtain optimum photoefficienciesfor the photoelectrclysis of water. The design constraints forsuch a material are presented and some results on a number of novel oxidesemiconductors are discussed in relation to their use in such photoelectrolysiscells.

Type of Award:DPhil Level of Award:Doctoral Awarding Institution: University of Oxford Notes:The digital copy of this thesis has been made available thanks to the generosity of Dr Leonard Polonsky


Goodenough, John B.More by this contributor



Hamnett, A.More by this contributor



Professor John GoodenoughMore by this contributor



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 Bibliographic Details

Issue Date: 1981Identifiers

Urn: uuid:59c30d35-ec19-4763-9d55-b85524ded79b

Source identifier: 602819595 Item Description

Type: Thesis;

Language: eng Subjects: Electrochemistry Electrodes Semiconductors Solar energy Energy storage Tiny URL: td:602819595


Autor: Dare-Edwards, M. P. - institutionUniversity of Oxford facultyMathematical and Physical Sciences Division - - - - Contributors Goo



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