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Thesis offer (eMOCA group) – From O2 electrochemical activation to the development of sustainable oxidation processes of organic substrates – Parisian Institute of Molecular Chemistry – UMR 8232
Oxidation chemistry in industrial processes constitutes a multimegaton commodity production valuing tens of billions dollars. The current economic and environmental contexts require to urgently replace the energy-demanding and harmful technologies often used with economically viable and environmentally sound alternatives.1 Through the reductive activation of O2, metalloenzymes, such as heme and nonheme Fe oxygenases achieve efficient and selective oxygenations by unravelling O2 oxidizing power. This is achieved through partial and controlled reduction of O2 bound at the Fe active site, involving sequential e– and H+ transfers to the Fe-oxygen adduct and formation of various oxidizing intermediates during the catalytic cycle.2 We have developed an electrochemical reductive O2 activation strategy and succeeded in mimicking the oxygenase activity by using Fe and Mn porphyrins to generate and to characterize various M-oxygen oxidizing species3 and to tune their reactivity.4 This original approach is part of the development of green electrosynthesis in an effort to electrify homogeneous catalysis.5
