Since the emergence of the first life forms on Earth, Nature has developed a plethora of strategies to activate and transform small molecules such as H2O, O2, CO2, etc. in order to store and use energy in the form of oxidant or reductant equivalents. One of its most successful strategies lies in the synchronization of several redox reactions orchestrated by a series of metal-enzymes. As a result of natural genetic mutations over the last four billon years, active sites of these metal enzymes evolved to perform optimized catalytic reactions with minimum energy consumption and high efficiency and selectivity. In these active sites, built around a metal center with an optimized geometry and redox properties, the second coordination sphere, constituted by amino acid residues, plays a major role in the reactivity of the enzyme. Among the most studied functionalities brought by these amino acid residues are substrate capture and orientation, proton and/or electron relay and reactive intermediates stabilization. Inspired by the active site of Carbon Monoxide Dehydrogenase (CODH), known to catalyze the reversible reduction of CO2 to CO, we developed new modified iron-porphyrin catalysts where functional groups were introduced in the second coordination sphere of the metal center.[1] Using our new catalysts, we were able to show that meticulous 3D positioning of these functional groups improves not only the energy efficiency of the catalytic electro-reduction of CO2 to CO but also the turnover frequency (TOF) while maintaining excellent selectivity. In one of the six biological CO2 sinks, the CO produced by the CODH is transported through gas channels to the Acetyl Coenzyme A (Acety-CoA) to be used in a carbonylation reaction. Applying a similar strategy, we were able to directly valorize the CO produced from a photocatalytic reduction of CO2 in carbonylation reactions for the preparation and the 14C radiolabeling of therapeutic drugs. [2]

Bioinspired strategy for the transformation and the valorization of carbon dioxide

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.