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Generating hydrogen using aromatic systems and metal catalytic centres.

Manton, Jennifer (2013) Generating hydrogen using aromatic systems and metal catalytic centres. PhD thesis, Dublin City University.

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Abstract

Chapter one presents a detailed literature survey which is relevant to the complexes which were developed for the generation of hydrogen, both photocatalytically and electrocatalytically in this thesis. Also discussed are the methods used throughout the research together with the principals of photophysics and electrochemistry. Chapter two begins with a short literature survey covering cobalt carbonyl complexes. The bonding, preparation and photochemistry of these complexes are discussed. Also included are cobalt complexes that have been reported in hydrogen generation. The synthetic procedures employed to prepare a number of alkynyl ligands and their cobalt hexacarbonyl and cobalt tetracarbonyldiphenylphosphinomethane derivatives are discussed. 1H NMR, 13C NMR, elemental analysis, UV-vis spectroscopy, IR spectroscopy, and fluorescence spectroscopy were used, where applicable. Time resolved infra-red spectroscopy experiments were also performed. This is the first time that time resolved studies have led to the detection of a CO loss species for an μ2-alkynyl cobalt carbonyl complex. The results of cyclic voltammetry studies are presented along with the results of both photocatalytic and electrocatalytic approaches for hydrogen generation. Chapter three begins with a concise literature survey focusing on the synthetic procedures which have been employed in the synthesis of boron-dipyrromethene (BODIPY) dyes and bis(dimethylglyoximato)cobaltIII (cobaloxime) complexes. Briefly discussed are the photochemical and electrochemical properties of some relevant BODIPY-cobaloxime systems. A number of BODIPYs photosensitisers and cobaloxime catalytic centres which have been used for the photogeneration and electrogeneration of hydrogen previously are included. The synthetic procedures employed to prepare two BODIPY dyes and the addition of cobaloxime to the ligands are discussed. 1H NMR, 13C NMR, elemental analysis, UV-vis spectroscopy, IR spectroscopy, and fluorescence spectroscopy were used. The results of cyclic voltammetry studies are presented along with the results of both photocatalytic and electrocatalytic hydrogen generation studies. xiii Chapter 4 begins with a short literature survey on the synthetic procedures which have been employed in the synthesis of porphyrin dyes and their attachment to bis(dimethylglyoximato)cobalt(III) (cobaloxime) which have been previously reported. Breifly discussed are the photochemical and electrochemical properties of some similar porphyrin-cobaloxime systems which have been reported by other groups. The synthetic procedures employed to prepare three porphyrin dyes and the additions of cobaloxime to the ligands are discussed. Again, 1H NMR, 13C NMR, elemental analysis, UV-vis spectroscopy and fluorescence spectroscopy were used, where applicable, to characterise the final pure products. The results of cyclic voltammetry studies are presented along with the results of both photocatalytic and electrocatalytic approaches for the generation of hydrogen.

Item Type:Thesis (PhD)
Date of Award:November 2013
Refereed:No
Supervisor(s):Pryce , Mary and Vos, Han
Uncontrolled Keywords:Hydrogen generation; Renewable energy sources
Subjects:Physical Sciences > Photochemistry
Physical Sciences > Chemistry
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:18149
Deposited On:26 Nov 2013 11:40 by Mary Pryce. Last Modified 08 May 2017 13:43

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