Development and Mechanistic Study of Well-defined Catalysts for the CO2 and H2O Reduction Reactions

Identifier:  TDX:3915

Handle: https://hdl.handle.net/20.500.11797/TDX3915

Authors:  Fernández Martín, Sergio

Abstract:
This doctoral thesis deals with the study of the reaction mechanisms involved in the reduction of CO2 and H2O catalyzed by first-row transition metal complexes. To this end, we have performed photocatalysis and electrocatalysis studies combined with chemical synthesis of reaction intermediates, in situ and ex situ spectroscopic studies, and computational studies by DFT. The first chapter introduces the most relevant aspects of molecular catalysis for the reduction of H2O and CO2, emphasizing the most recent mechanistic findings in the field of electrocatalytic reduction of CO2. Chapter II is dedicated to the evaluation of the electronic effects on the ligand in the photocatalytic activity of water reduction of polypyridylamine Co complexes. The following two chapters (III and IV) deal with the mechanistic study of the family of CO2 reduction catalysts under photochemical, electrochemical and (photo)electrochemical conditions. Chapter V focuses into the investigation of an Mn(I) tricarbonyl molecular electrocatalyst based on an Nheterocyclic biscarbene ligand and its role in the reduction of CO2 to CO and formate. Finally, chapter VI introduces a new family of organometallic systems based on a tris(phosphino)alkyl ligand with C3 symmetry and its Ni(II) complexes. These complexes are stable, active and highly selective towards the production of CO by CO2 reducion