Mimicking the second coordination sphere and up to the outer sphere of metalloenzymes with molecular electrode materials for protons and CO2 electrocatalytic reduction – InnovMat

It is now becoming clear that the only way to obtain even more efficient molecular catalysts, with an activity that could approach the exceptional performance of metalloenzymes, is to act on the interactions of the catalyst with its microenvironment beyond the first coordination sphere, i.e. from the second to the outer sphere. InnovMat aims to develop innovative bio-inspired molecular electrode materials for protons and CO2 reduction based on a polymer matrix that will include different functionalities found in enzymes working in synergy for optimal catalytic activity: a molecular active center with influent/proactive chemical functions in the second coordination sphere and additional functions in the polymer matrix for the outer sphere, in order to promote proton transfers and stabilization of metal intermediates. As molecular catalysts, we will use the highly promising but still under-exploited family of cobalt catalysts with a macrocyclic ligand. Our systematic, step-by-step approach to increasingly sophisticated systems will provide a unique opportunity to obtain relevant information on the influence of the microenvironment (second coordination sphere to the outer sphere) on catalytic activity for molecular complexes in homogeneous and heterogeneous phases, in order to achieve a global understanding of catalysis beyond the first coordination sphere. This project also tackles one of the current challenges for molecular catalysts: the development of efficient heterogenization approaches by addressing the main pitfalls of current techniques, including a high and adjustable number of active sites by electropolymerization and the prevention of the leaching in solution due to the covalent attachment of the catalyst to the polymer.