Geraty, Suzanne M (1989) Ruthenium-containing polymers-synthesis, characterisation and electrochemical properties. PhD thesis, Dublin City University.
Abstract
In this work, the synthesis and characterisation of a
series of ruthenium-containing metallopolymers based
on poly-H-vinylimidazole are reported, with a view to
subseguently investigating their electrochemical
properties and potential applications of electrodes
modified with these polymers. The prepared complexes
were characterised using spectroscopic and
electrochemical techniques. It was found that the
products, or ratios of products, obtained depended on
the reaction conditions, i.e. polymer:metal ratios,
reflux time and reaction solvent. The two main
products obtained were of the from
[Ru (bipy) 2 (PNVI) Cl ] ’r and [Ru(bipy} 2 (PNVI) 2 ] > The
electrochemical properties of these materials were
examined as films on the surface of glassy-carbon
electrodes. Sweep-rate dependence, electrolyte
dependence and film stability were subsequently
studied. The electrochemical response was found to
depend strongly on the nature of the supporting
electrolyte. Glassy-carbon electrodes coated with
methanolic solutions of [Ru(bipy) n (PNVI'Cl] and
fRu(bipy)(PNVI) 2 ] were used to study the
photochemical properties of these materials.
Electrolyte dependence was again found to be very
significant,, both as a function of the reaction
product and as a function of film stability.
[Ru.(bipy) ( PNVI) Cl]was found to exhibit interesting
phor.ochem.rcal properties, particularly in sulphatebased
electrolytes where a photostable sulphate
intermediate complex was found to form. This lends
possibilities to potential applications in switching
devices. The photoresponsive properties of
[ Ru(bipy) 2 (PNVI) p ] have also been investigated in
the presence of' suitable external quenchers. The
diffusion co-efficient of the electron in the film was
investigated using the technique of chronoamperometry. The charge-transport diffusion coefficient was
determined to be of the order of 10’ cm s' . The
mediating properties of the monosubstituted complex
were studied. This complex v/as found to catalyse the
oxidation of Fe(II) to Fe (III) is aqueous solution.
Two substrates, (NH^)2Fe(SO) 2 and K^Fe(CN)g were
studied for this purpose. ^ Electrolyte and film
thickness were found to be important features in the
results obtained for these studies. All results
obtained were compared to similar results previously
obtained for polyvinylpyridine based analogues.
Metadata
Item Type: | Thesis (PhD) |
---|---|
Date of Award: | 1989 |
Refereed: | No |
Supervisor(s): | Vos, Johannes G. |
Uncontrolled Keywords: | Ruthenium; Polymers |
Subjects: | Physical Sciences > Electrochemistry |
DCU Faculties and Centres: | DCU Faculties and Schools > Faculty of Science and Health > School of Chemical Sciences |
Use License: | This item is licensed under a Creative Commons Attribution-NonCommercial-No Derivative Works 3.0 License. View License |
ID Code: | 18747 |
Deposited On: | 30 Jul 2013 10:42 by Celine Campbell . Last Modified 30 Jul 2013 10:42 |
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