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Calixarènes pour la synthèse radiolytique de nanoparticules métalliques

Abstract : During this thesis, the synthesis of different calix[8]arenes and mono- and bimetallic calixarenic complexes was performed in order to produce nanoparticles by radiolysis. The different steps of the synthesis were optimized and different functionalizations were tested to improve the solubility and the anchoring at the nanoparticles surface. Metallic nanoparticles were generated from silver and/or gold salts and stabilized by calix[8]arenes in ethanol. The obtained spherical nanoparticles were very small (less than 5 nm) and homogeneous in size. HAADF/STEM-EDS analyses performed on Au-Ag nanoparticles revealed their bimetallic character and the presence of very small aggregates of less than 1 nm. Catalyticefficiency of the silver nanoparticles was tested through nitreous compound reduction.These results show the calixarenes efficiency to stabilize small nanoparticles while allowing the catalytic activity. Mono- and bimetallic nanoparticles (Au and Au-Ag) were also synthesized by radiolysis from the calixarenic complexes. This synthetic pathway allowed the increase of the amount of metal used during the synthesis without increasing the size of the obtained nanoparticles (3-4 nm). This particularity can be related to fast exchange phenomena between clusters formed by the calixarenes and the metallic precursors complexes, that were shown by NMR spectroscopy. However, this NMR study needs to be pursued.
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Marie Clément. Calixarènes pour la synthèse radiolytique de nanoparticules métalliques. Chimie théorique et/ou physique. Université Paris Saclay (COmUE), 2017. Français. ⟨NNT : 2017SACLS449⟩. ⟨tel-01885500⟩

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