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Scientific result | Green Chemistry | Bio-inspired catalysis | Carbon cycle
By studying the structure-reactivity relationships of bio-inspired catalysts for CO2 reduction, researchers from I2BC (SB2SM) and ICMMO have shown that the effects of through-space electrostatic interactions surpass the through-bonds electronic effects. A further step towards obtaining a durable catalyst to reduce the atmospheric accumulation of CO2, responsible for global warming.
To reduce the atmospheric accumulation of CO2, a major cause of global warming, it would be necessary to massively and durably transform CO2 into fuel or synthetic bricks, a real challenge for chemists. To address this, they can draw inspiration from particularly effective natural metallo-enzymes, such as carbon monoxide dehydrogenase, which reversibly reduces CO2 to CO. In this context, the Photocatalysis and Biohydrogen team led by Winfried Leibl (SB2SM), in collaboration with ICMMO*, has been developing, for several years, a family of bio-inspired catalysts of the iron porphyrin type, particularly promising for the catalytic electro-reduction of CO2 (see Joliot highlight of 2020).
In enzymes, according to the work of Arieh Warshel, Nobel laureate in chemistry in 2013, through-space electrostatic interactions play a major role in the activation of substrates, by stabilizing intermediates. What about bio-inspired catalysts? To answer this question, in this study, the researchers designed and synthesized a series of iron porphyrins, mono- and tetra-substituted by cationic imidazolium groups in the second coordination sphere. They also compared the effects of through-space electrostatic interactions to through-structure electronic effects by synthesizing a derivative containing a single imidazolium and six fluorine atoms in the form of electron withdrawing groups (Figure).
The study of the catalytic properties (over-potential and TOF **) of these derivatives has demonstrated the additive effect of electrostatic interactions on the catalytic properties of iron porphyrins: while the over-potential of these catalysts decreases when the number of imidazolium units increases, a gain of six orders of magnitude for the TOFs is observed when switching from the tetra- catalyst to the monosubstituted catalyst. In parallel, the results obtained with the derivative comprising fluorine atoms indicate that the effects of through-space electrostatic interactions surpass the classical through-structure electronic effects.In conclusion, as part of the quest for durable catalytic systems for CO2 reduction, this work has improved our understanding of the structure-reactivity relationships of bio-inspired catalysts, necessary for obtaining the combination of chemical functions generating optimized catalytic properties.
This work has been published in ChemSusChem as a "Very Important Paper" and has been the subject of the journal's cover (issue 5/2021).
* ICMMO : Institut de Chimie Moléculaire et des Matériaux d'Orsay.
** The over-potential (in mV) corresponds to the additional electrical potential that must be applied in relation to the thermodynamic potential of the reaction. The TOF (turnover frequency) corresponds to the frequency of renewal of the reaction (in s-1).
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A Khadhraoui, P Gotico, W Leibl, Z Halime, A Aukauloo. Through-Space Electrostatic Interactions Surpass Classical Through-Bond Electronic Effects in Enhancing CO2 Reduction Performance of Iron Porphyrins. ChemSusChem, 2021, https://dx.doi.org/10.1002/cssc.202002718
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.