Institut de Chimie Moléculaire et des Matériaux d'Orsay

Chimie Inorganique

Photosynthèse artificielle


Animé par Zakaria Halime (


Recent advances in metalloporphyrin-based catalyst design towards carbon dioxide reduction: from bio-inspired second coordination sphere modifications to hierarchical architectures. P. Gotico, Z. Halime, A. Aukauloo (2020) Dalton Trans. 49, 2381


Research in the development of new molecular catalysts for the selective transformation of CO2 to reduced forms of carbon is attracting enormous interest from chemists. Molecular catalyst design hinges on the elaboration of ligand scaffolds to manipulate the electronic and structural properties for the fine tuning of the reactivity pattern. A cornucopia of ligand sets has been designed along this line and more and more are being reported. In this quest, the

porphyrin molecular platform has been under intensive focus due to the unmatched catalytic properties of metalloporphyrins. There have been rapid advances in this particular field during the last few years wherein both electronic and structural aspects in the second coordination spheres have been addressed to shift the overpotential and improve the catalytic rates and product selectivity. Metalloporphyrins have also attracted much attention in terms of the elaboration of hybrid materials for heterogeneous catalysis. Here too, some promising activities have made metalloporphyrin derivatives serious candidates for technological implementation. This review collects the recent advances centered around the chemistry of metalloporphyrins for the reduction of CO2.


Spectroscopic Characterization of Bio-inspired Ni-based Proton Reduction Catalyst Bearing Pentadentate N2S3 Ligand with Improved Photocatalytic Activity. P. Gotico, D. Moonshiram, C. Liu, X. Zhang, R. Guillot, A. Quaranta, Z. Halime, W. Leibl, A. Aukauloo (2020) Chem. Eur. J. 26, 2859-2868




Inspired by the sulphur-rich environment of [NiFe] hydrogenase, a novel Ni-based proton reduction catalyst bearing an acyclic pentadentate N2S3 ligand has been shown to improve photocatalytic activity and has been mechanistically probed by time-resolved optical and X-ray absorption spectroscopy. 




Second‐Sphere Biomimetic Multipoint Hydrogen‐Bonding Patterns to Boost CO2 Reduction of Iron Porphyrins. P. Gotico, B. Boitrel, R. Guillot, M. Sircoglou, A. Quaranta, Z. Halime, W. Leibl, A. Aukauloo (2019) Angew. Chem. Inter. Ed. 58, 4504-4509 (10.1002/anie.201814339)


Like CODH: Urea groups at an iron porphyrin catalyst give multipoint hydrogenbonding stabilization resembling that found in the CO2 adduct of carbon monoxide dehydrogenase (CODH). The catalyst gave improved CO2 reduction to CO. Entrapped water molecules within the molecular clefts were found to be the source of protons for the CO2 reduction.



Local Ionic Liquid Environment at a Modified Iron Porphyrin Catalyst Enhances Electrocatalytic Performance of CO2 to CO Reduction in Water. A. Khadhraoui, P. Gotico, B. Boitrel, W. Leibl, Z. Halime, A. Aukauloo (2018) Chem. Comm. 54, 11630-11633


In this study, we report a strategy to attach methylimidazolium fragments as ionic liquid units on an established iron porphyrin catalyst for the selective reduction of CO2 to CO. Importantly, we found that the tetra-methylimidazolium containing porphyrin exhibits an exalted electrocatalytic activity at low overpotential in water precluding the need for an external proton donor.



Visible-Light-Driven Reduction of CO2 to CO and Its Subsequent Valorization in Carbonylation Chemistry and 13C Isotope Labeling. P. Gotico, A. Del Vecchio, D. Audisio, A. Quaranta, Z. Halime, W. Leibl, A. Aukauloo (2018) ChemPhotoChem 2, 715-719


Reduce, reuse, recycle: A CO2 valorization strategy based on its photocatalytic reduction to CO and the direct use of the produced CO in a palladium‐catalyzed aminocarbonylation reaction is reported. This approach provides a means for more efficient application of 13C‐isotope and 14C‐radioisotope‐labeled CO2 in pharmaceutically relevant drug labeling.



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Dernière mise à jour le 04.05.2020