Novel catalysts for the electro- and photoelectrochemical CO2/H2O transformation for chemicals production

Identifier:  TDX:4045

Handle: https://hdl.handle.net/20.500.11797/TDX4045

Authors:  Miró Serra, Roger

Abstract:
Based on the dependance of the fossil fuels consumption this thesis is focused on the development of processes using renewable energies, i.e., involving electrochemical and photoelectrochemical steps, for the transformation of raw materials, such as CO2 and H2O, to added value chemicals. Based on the state of the art, the first part of the thesis is focused on study the synergism of the ionic liquid with the iron porphyrin catalyst, to electrochemically reduce CO2 to produce CO with improved catalytic performances at lower overpotentials. The generated CO is in-situ used in tandem processes to obtain added value organic compounds by Pd-catalyzed carbonylation and, for the first time, Rhcatalyzed hydroformylation reactions. The second part, reports the preparation of hybrid photocathodes via the immobilization by electropolymerization of a new series of synthetized Ru and Re based organometallic complexes onto two different semiconductors, Cu2O/SnO2 and CuGaO2. These electrodes have been applied in the photoelectrochemical CO2 reduction to formic acid revealing the crucial role in the catalytic performance of the electrolyte and the prepared hybrid photocathodes. Finally, in the last part of the thesis is described the preparation of different Ru based organometallic complexes and their immobilization onto BiVO4. Two different immobilization approaches, electropolymerization and thiol-ene click reaction, are described. The different prepared hybrid photoanodes are tested in the water oxidation reaction showing an improvement compared with the bare BiVO4.