Bio-inspired iron complexes for oxidation catalysis : homogeneous and supported systems

Some metalloenzymes catalyze oxidation of small organic molecules in mild conditions (via dioxygen activation at ambient temperature and pressure). This work aims to improve the use and catalytic efficiency of some of the iron complexes mimicking this activity.First, by ligand functionalization, one of the most efficient complexes catalyzing aromatic substrates oxidation by H2O2, was grafted in mesostructured porous silicas. This type of materials was used to support the iron catalyst, because of their large specific area, as well as their versatile surface chemistry. Furthermore, the method of synthesis allows to tune the size of cavities, through the use of surfactant as templates. Control of the number of catalytic sites on surface is made possible by the procedure that exploits the molecular stencil patterning technique. The confinement of catalyst in the pores could be implemented to form products with high added value. In parallel, this complex was also grafted in fumed silicate, a simpler material, that could be used to degradation of polluants. The development of this type of supported catalyst required many caracterisations : elemental analysis, NMR, IR, XPS, UV-vis and EPR spectroscopies, TGA, nitrogen sorption isotherms, powder X-ray diffraction. Different grafting methods have been followed, and their efficacy compared. The catalytic activity of the different systems was also evaluated.Concerning the development of homogenous catalysts, the strengthening of pyridine  positions on the ligand has allowed to obtain new iron complexes, having a better stability to realize catalytic reactions in homogenous condition, and structural, spectroscopic, chemical, catalytic properties similar to the complexes of the same family.Finally, another iron complex has been applied in an electrochemical process using dioxygen in the presence of proton to catalyze hydroxylation of aromatic substrates.

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Source https://theses.hal.science/tel-00915279
Author Jollet, Véronique
Maintainer CCSD
Last Updated May 7, 2026, 22:08 (UTC)
Created May 7, 2026, 22:08 (UTC)
Identifier NNT: 2011PA112270
Language fr
Rights https://about.hal.science/hal-authorisation-v1/
contributor Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO) ; Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS)
creator Jollet, Véronique
date 2011-12-06T00:00:00
harvest_object_id e898c873-9ce1-491a-ad30-402146396596
harvest_source_id 3374d638-d20b-4672-ba96-a23232d55657
harvest_source_title test moissonnage SELUNE
metadata_modified 2026-03-30T00:00:00
set_spec type:THESE