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Complexes de cobalt(I) : synthèse raisonnée de nanocristaux mono- ou bimétalliques et applications catalytiques

Abstract : Nanocatalysis universe is a field which is yet to be explored, especially because of the difficult access to simple and well-controlled nanoparticles and their uses in heterogeneous catalyzed reactions. In this work, we show that it is possible to obtain hcp cobalt nanoparticles starting from the easily accessible CoCl(PPh3)3 and by simply heating it in oleylamine. The mechanism of this reaction based on the disproportionation of the cobalt(I) was proved by experimental and theoretical studies. We also demonstrate that it is possible to control the size and the shape of those nanoparticles by changing some parameters like the reaction time or the nature of the organometallic precursor. Moreover, by using the same protocol with other metals (especially nickel) we were able to obtain nanoparticles and then to form CoxNi1-x bimetallic alloys. Our nanoparticles were used for hydrogenation and hydrogen transfer reactions in presence of NH3BH3 (mainly on alkynes) giving good conversions and selectivities. We then compare those results with homogeneous catalysis, using different cobalt complexes. We made an in-depth study of this homogeneous catalysis which shows once again the efficiency of cobalt (as nanoparticles or organometallic complexes) on hydrogenations and hydrogen transfers. Those results offer new opportunities concerning the use of non-noble metals for the storage and the use of dihydrogen, allowing easier access towards energy applications.
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  • HAL Id : tel-02479575, version 1


Anthony Vivien. Complexes de cobalt(I) : synthèse raisonnée de nanocristaux mono- ou bimétalliques et applications catalytiques. Chimie organique. Sorbonne Université, 2018. Français. ⟨NNT : 2018SORUS235⟩. ⟨tel-02479575⟩



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