Nanocatalysts for sustainable industrial processses

In Chapter 1, rhodium nanoparticles were supported on multiwalled carbon nanotubes (MWCNTs) and bound to the magnetic core-shell system Fe3O4@TiO2. The composite Fe3O4@TiO2-Rh-MWCNT and the intermediates were characterized by SEM, EDS and TEM. Their catalytic activity was studied using i) the hydrogenation transfer of nitroarenes and cyclohexene in the presence of hydrazine hydrate; ii) the reduction of 2-nitrophenol with NaBH4; and iii) the decoloration of pigments in the presence of hydrogen peroxide. The results were monitored by gas chromatography (i) and UV Visible (ii and iii). In the second chapter, the catalytic activity of six oxidovanadium(V) aroylhydrazone complexes, viz. [VOL1(OEt)][VOL1(OEt)(EtOH)] (1), [VOL2(OEt)] (2), [Et3NH][VO2L1] (3), [VO2(H2L2)]2·EtOH (4), [VOL1(µ -O)VOL1] (5) and [VOL2(µ -O)VOL2] (6) (H2L1 = 3,5-di-tert-butyl-2-hydroxybenzylidene)-2hydroxybenzohydrazide and H2L2 = 3,5-di-tert-butyl-2-hydroxybenzylidene)-2 aminobenzohydrazide), anchored on nanodiamonds with different treatments, was studied towards the microwave-assisted partial oxidation of 1-phenylethanol to acetophenone in the presence of tert-butyl hydroperoxide (TBHP) as oxidant. A high selectivity for acetophenone was achieved for the optimized conditions. The possibility of recycling and reuse the heterogeneous catalysts was also investigated. In chapter 3, the catalytic activity of gold nanoparticles supported at different metal oxides, such as Fe2O3, Al2O3 ZnO or TiO2, was studied for the above reaction. The effect of the support, quantity of the catalyst and temperature was investigated. The recyclability of the gold catalysts was also studied. In the last chapter, a new copper nanocomposite with functionalized mutiwalled carbon nanotubes (Cu-MWCNT) was synthesized using a microwave assisted polyol method. The characterization was performed using XRD and SEM. The catalytic activity of Cu-MWCNT was studied through the degradation of pigments, such as amaranth, brilliant blue, indigo, tartrazine and methylene blue.

New metallomolecular wires based on carbon-rich bridging systems: a systematic study

This dissertation presents and discusses the preparation of molecular wires (MW) candidates that would then be probed for electron transfer properties. These wires are bridged by 1,4-diethynylbenzene derivatives with alkoxy side chains with palladium and ruthenium metal complex termini. Characterization of these compounds was performed by usual spectroscopic techniques like 1H, 13C{1H} and 31P{1H} NMR, MS, FTIR and UV-Vis as well as by cyclic voltammetry which allowed classifying the candidates in the Robin–Day system and determination of bridges side chain and length effects on electronic transport. Preparation of the 1,4-diethynylbenzene derivatives was done with synthetic pathways that relied heavily in palladium catalyzed cross-couplings (Sonogashira). A family of single ringed 1,4-diethynylbenzene ligands with different length alkoxy side chains (OCH3, OC2H5, OC7H15) was thus prepared allowing for the influence of these ring decorations to be assessed. The ruthenium binuclear rods showed communication between metal centres only when the shorter ligands were used whereas the longer Ru complexes showed only one redox pair in CV studies which is in agreement to non-communicating metal centres. Cyclic voltammetry studies show irreversible one wave processes for palladium dinuclear complexes, making these rods function as molecular insulators. Fluorescence decay studies performed on the prepared compounds (ligands and complexes) show a pattern of decreasing decay times upon coordination to the metal centres which can due to ligand charge redistribution upon coordination leading to non-radiative relaxation paths. Regarding the X-ray structures, two new ligand related structures were obtained as well as new structure for a palladium rod. The effect of the side chains was observed to be important to the wires’ electronic properties when comparing with the analogues without a side chain. The effect brought by longer chains is nevertheless almost negligible.