Cathodic corrosion is a relatively unknown phenomenon that can severely etch metallic electrodes at cathodic (negative) potentials. In spite of these remarkable changes that are caused by cathodic... Show moreCathodic corrosion is a relatively unknown phenomenon that can severely etch metallic electrodes at cathodic (negative) potentials. In spite of these remarkable changes that are caused by cathodic corrosion, the phenomenon is stil not fully understood. Cathodic corrosion is therefore the focus of this PhD thesis. The first three experimental chapters of the thesis focus on characterizing platinum, rhodium and gold electrodes before and after cathodic corrosion in a variety of working solutions. In doing so, these chapters establish surprisingly mild corrosion onset potentials and reveal an etching anistropy that depends on the cation in the working solution. Additional density functional theory calculations suggest a similarly significant role for adsorbed hydrogen. These result suggest the existence of ternary metal hydrides during cathodic corrosion. The role of hydrides is further studied in the fourth experimental chapter through X-ray absorption spectroscopy. These four fundamental chapters are followed by two more applied chapters. The first of these tailors the activity of a platinum single crystal towards oxygen reduction, by using cathodic corrosion. The second applied chapter uses cathodic corrosion to create and thoroughly characterize alloyed nanoparticles. Combined, these fundamental and applied chapters provide valuable new information towards understanding and applying cathodic corrosion. Show less
With the energy transition toward a renewable energy supply and a CO2-neutral economy, electrification of the energy system is rising in importance, which leads to the challenge of long-term... Show moreWith the energy transition toward a renewable energy supply and a CO2-neutral economy, electrification of the energy system is rising in importance, which leads to the challenge of long-term storage of renewable electricity. A promising option is the electrochemical conversion of biomass or carbon dioxide in chemicals as energy carrier. In this research, catalysis of the electrochemical CO2 reduction was studied to obtain liquid fuels. In this fundamental study we discovered that so-called disproportionation reactions may occur simultaneously with the CO2 reduction reaction influencing the product spectrum. Moreover, we focused on metalloprotoporphyrins immobilized on a graphite surface. We found that the selectivity can be steered toward formic acid with rhodium, tin or indium metal centers. Apart from intrinsic catalyst parameters, we studied the influence of parameters related to the immobilization and the composition of the electrolyte. We showed that the substrate and its pretreatment as well as encapsulation of the catalyst in polymers can have a signifcant influence on the electrocatalysis of CO2 reduction. The results obtained in this thesis provide insight in the energy efficiency, reaction rate and selectivity of the CO2 reduction reaction, and play an important role for the development of an industrially viable process. Show less
The electrochemical oxidation of ammonia to dinitrogen is a model reaction for the electrocatalysis of the nitrogen cycle, as it can contribute to the understanding of the making/breaking of NN, NO... Show moreThe electrochemical oxidation of ammonia to dinitrogen is a model reaction for the electrocatalysis of the nitrogen cycle, as it can contribute to the understanding of the making/breaking of NN, NO, or NH bonds. Moreover, it can be used as the anode reaction in ammonia electrolyzers for H2 production or in ammonia fuel cells. We study here the reaction on the N2-forming Pt(1 0 0) electrode using a combination of electrochemical methods, product characterization and computational methods, and suggest a mechanism that is compatible with the experimental and theoretical findings. We propose that N2 is formed via an ∗NH + ∗NH coupling step, in accordance with the Gerischer-Mauerer mechanism. Other NN bond-forming steps are considered less likely based on either their unfavourable energetics or the low coverage of the necessary monomers. The NN coupling is inhibited by strongly adsorbed ∗N and ∗NO species, which are formed by further oxidation of ∗NH. Show less
In this dissertation, the synthesis and characterization of a series of iron complexes based on different ligand platforms are described. The complexes are subsequently studied for their... Show moreIn this dissertation, the synthesis and characterization of a series of iron complexes based on different ligand platforms are described. The complexes are subsequently studied for their activity in catalytic water oxidation with the help of a variety of electroanalytical techniques. The results show that the catalytic activity of structurally related iron complexes correlates strongly with the electronics of the iron centre. Another potentially very important aspect in the field of homogeneous electrocatalysis which has so far received only very little attention in published literature is the influence of the nature of the electrode material on the resulting electrochemistry. The results discussed in thesis show that interactions between the working electrode and the catalyst in solution can exhibit a strong influence on the resulting electrochemistry. Overall, the results of this work demonstrate that iron-based complexes can indeed be made to work as electrocatalysts for the water oxidation reaction. Furthermore, the results show that the electronic structure of the iron centre is a promising target for the design of new and improved catalysts. Finally, the results also highlight the importance of trying out different electrode materials as part of routine tests of new potential electrocatalysts. Show less
