Water oxidation From Molecular Systems to Functional Devices
Abstract: The production of hydrogen gas, through the process of water splitting,is one of the most promising concepts for the production of clean andrenewable fuel.The introduction of this thesis provides a brief overview of fossil fuelsand the need for an energy transition towards clean and renewable energy.Hydrogen gas is presented as a possible candidate fuel with its productionthrough artificial photosynthesis, being described. However, the highlykinetically demanding key reaction of the process – the water oxidationreaction – requires the use of a catalyst. Hence, a short presentation of differentmolecular water oxidation catalysts previously synthesized is also provided.The second part of the thesis focuses on ruthenium-based molecularcatalysis for water oxidation. Firstly, the design and the catalytic performancefor a new series of catalysts are presented. Secondly, a further study onelectron paramagnetic resonance of a catalyst shows the coordination of awater molecule to a ruthenium centre to generate a 7-coordinated complex atRuIII state. Finally, in an electrochemical study, coupled with nuclear magneticresonance analysis, mass spectrometry and X-ray diffraction spectroscopy, wedemonstrate the ability of a complex to perform an in situ dimerization of twounits in order to generate an active catalyst.The final part of this thesis focuses on immobilisation of first rowtransition metal catalysts on the surface of electrodes for electrochemical wateroxidation. Initially, a copper complex was designed and anchored on a goldsurface electrode. Water oxidation performance was studied byelectrochemistry, while deactivation of the electrode was investigated throughX-ray photoelectron spectroscopy, revealing the loss of the copper complexfrom the electrode during the reaction. Finally, we re-investigated cobaltporphyrin complexes on the surface of the electrode. Against the backgroundof previous report, we show that the decomposition of cobalt porphyrin intocobalt oxide adsorbed on the surface is responsible for the catalytic activity.This result is discussed with regard to the detection limit of various spectroscopic methods.
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