Molecular Engineering of Electrode Surfaces for Electrocatalysis

Electrocatalysts play an important part on the route towards environmental friendly energy sources. They support modern technologies like fuel cells to move further away from the utilization of fossil fuels and the resulting CO2 emission into our atmosphere. The main principle of such energy conversion technologies is to store chemical energy within chemical bonds and to release it as electric energy to fulfill the energy demand of today's society. However energy conversion chemistry in such technologies requires catalysts in order to be effective by providing an alternative reaction pathway that lowers activation energies and maximizes the energy output. Providing suitable catalyst surfaces requires a fundamental knowledge of the interaction of reactants and reaction intermediates with the catalyst surfaces. This concern is addressed in this thesis by fabricating specifically tailored molecular components on metal surfaces, which act as organic/inorganic hybrid electrodes for various energy conversion reactions in electrocatalysis. Characterizing the electrode surface is crucial in order to identify active sites of the catalyst. The molecular structure is investigated by surface sensitive techniques, such as STM and XPS in combination with a home-build transfer system, which enables electrode fabrication in UHV and electrocatalytic experiments in a liquid environment. A detailed characterization of organic polymer components on electrode surfaces is obtained by combining experimental data with MD simulations. The morphology of polymer networks can be successfully mimicked and depending on the chemical composition and the structure, spatial correlations on short length scales are reported. Hybrid electrodes with organic polymer co-catalysts reveal an increased catalytic activity for the HER by providing suitable docking sites that act as catalytic active sites. Reactants and reaction intermediates are stabilized via hydrogen bonding, which results in a higher catalytic turnover. The specific designed structure of the organic co-catalyst helps to identify a fraction of the reaction mechanism and highlights the importance of molecular components in electrocatalysis. The utilization of organic units on electrocatalysts provides also an excellent opportunity in order to use single metal atoms as catalysts. Engineering large pi-systems has no significant impact on the ORR activity, while the distance between active sites and the underlying electrode are crucial for enhancing the catalytic activity. A significant factor in using molecular components in electrocatalysis is the stability of the organics. Using electrografting allows to design organic/inorganic hybrid electrodes with covalent bonds between the molecular component and the metal substrate. Attaching empty porphyrin molecules to substrates introduces a powerful technique in molecular engineering, since empty porphyrin cycles can be metallized with various metal centers that can act as electr