Felicia Zaar: Heterogeneous Molecular Catalysis: Experimental and Computational Considerations

Abstract

The transition towards a society free from emission of CO2 hinges on the replacement of fossil fuels by more eco-friendly alternatives. An attractive option is the H2 economy, in which fuel production and usage are enclosed in a sustainable water-to-water cycle consisting of fuel cells and solar-driven water electrolysis. A major obstacle to large-scale implementation of such a cycle is the cost and availability of catalysts that promote the associated redox reactions, including the hydrogen evolution reaction (HER). Therefore, this thesis explores the possibilities of applying molecular structures as catalysts toward the HER, and of making these catalysts industrially appealing by incorporating them into a conducting polymer directly attached to an electrode surface. If successful, the resulting materials - conducting redox polymers - would constitute efficient, selective and scalable catalytic materials made from earth-abundant elements. This work presents a thorough electrochemical characterization of conducting redox polymers aimed at catalytic applications, alongside experimental and computational mechanistic studies of metalloporphyrins employed as electrocatalysts toward the HER.