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Scientific result | Bio-inspired catalysis
A team from I2BC (SB2SM), in collaboration with ICMMO, optimized a bio-inspired CO2 reduction catalyst, designed and developed in the laboratory, and showed that its efficiency relies on a subtle balance between CO2 fixation at the catalytic site and access to protons, which is essential for breaking the C=O bond.
Recycling carbon dioxide would reduce its atmospheric accumulation, one of the main causes of global warming. To turn CO2 into fuel or building blocks for organic compounds of interest, we must first break the O=C=O bonds, a very energy-consuming process. For this, researchers can draw inspiration from nature, which posess particularly effective metalloenzymes, such as carbon monoxide dehydrogenase, which reversibly reduces CO2 to CO.In 2019, the I2BC team developed a new iron porphyrin* type catalyst, directly inspired by the active site of carbon monoxide dehydrogenase and particularly promising for reduction of carbon dioxide. More precisely, the researchers had modified the iron porphyrin by introducing, on its second coordination sphere, urea functions, acting as molecular pillars providing hydrogen bonds to immobilize the CO2 on the metal center, as in the natural enzyme (Gotico et al., Angew.Chemie, 2019).In order to enhance the energy and kinetic performance of this catalyst, the researchers studied here the impact of the topology of urea groups on the electro-catalytic reduction of CO2. For this, two isomers of the catalyst comprising two urea groups were synthesized and their catalytic properties characterized: in the first isomer, the two urea groups face each other on the same side of the porphyrin cycle (alpha alpha), whereas in the second, the two urea groups are in trans, on either side of the porphyrin cycle (alpha beta).The obtained results show that the modification of the second coordination sphere of the catalyst impacts its functional properties (figure). Indeed, if the alpha alpha isomer possesses a better affinity for CO2 than the alpha beta isomer, the latter has better catalytic activity with the best rate constant reported in the literature for the electro-catalytic reduction of CO2 to CO. The authors attribute this observation to a more efficient protonation step of CO2 during its reduction. In fact, when the CO2 molecule is trapped between the two urea groups in the case of the alpha alpha isomer, this step is very slowed down whereas in the case of the alpha beta, isomer, the CO2 molecule is held by only one hydrogen bonded arm thus allowing the proton access for the conversion of CO2 into CO.
In conclusion, this study tells us that a better catalysis of CO2 reduction requires a subtle control of its fixation at the catalytic site and of access of protons, an essential ingredient for the rupture of the C=O bond.Contact : email@example.com* An iron porphyrin is a molecule with a macrocyclic structure, like the heme of hemoglobin, which is used to fix oxygen in red blood cells.
P. Gotico, L. Roupnel, R. Guillot, M. Sircoglou, W. Leibl, Z. Halime, A. Aukauloo. Atropisomeric Hydrogen Bonding Control for CO2 Binding and Enhancement of Electrocatalytic Reduction at Iron Porphyrins. Angewandte Int. Ed. 2020 https://doi.org/10.1002/anie.202010859
CEA is a French government-funded technological research organisation in four main areas: low-carbon energies, defense and security, information technologies and health technologies. A prominent player in the European Research Area, it is involved in setting up collaborative projects with many partners around the world.