Theoretical models for the electrochemical reduction of CO2 on copper catalysts under working conditions

CO2 reduction is the only process which can generate green fuels with a net negative impact in CO2 emissions. Therefore, the future development of our society needs an industrial scale up of this technology, involving the production of heavily used chemicals such as ethylene. Copper is a unique material for catalyzing these C2+ products, however significant advances need a deep theoretical understanding of the complexity of this material under CO2 reduction conditions. In this thesis I aimed at developing theoretical methods to address the main factors involved in this process: (i) surface reconstruction at negative potential; (ii) chemical effects on copper selectivity; and (iii) the effect of the electrolyte. Chapters I and II were dedicated to the motivations and methods. After having benchmarked in Chapter 3 well-established experimental results, such as the morphology dependence of CO2 product distribution on copper local morphology, I investigated the reconstruction of polycrystalline copper at negative potentials. This process is driven by local surface polarization, which destabilizes close-packed domains and promotes (100) facets and defects. Following theoretical guidelines, I synthesized an effective copper-based catalyst with produced ethylene at high yield and high current density. In Chapter V I studied a complex oxide-derived copper material to provide insights about copper oxidation state, its coordination and surface ensembles active toward C2+ chemicals. Among the outcomes, I demonstrated that polarization drives CO2 reduction activity, whilst a newly reported intermediate, a deprotonated glyoxylate, triggers C2+ selectivity. In chapter VI I dedicated to chemical effects on copper reactivity. Sulfur adatoms, acting as strong tethering centers enable the generation of formate, a chemical employed as preservative for animal food stock. Finally, in Appendix A I introduced cation effect on CO2 reduction, not yet fully understood but having a clear relevance on product distribution.