Rational design of molecular water oxidation catalysts

In this thesis I will describe my contributions to the field of molecular water oxidation catalysis. In Chapter 1 a broad introduction into the field of water oxidation catalysis is given, starting off with the societal relevance of this research in relation to climate change and renewable energy storage. Chapter 2 discusses scaling relations in molecular catalysts for water oxidation and their influence on the fundamental minimal overpotential that can be achieved depending on the mechanism by which the water oxidation catalyst operates. In Chapter 3 an iridium water oxidation catalyst is described that oxidatively anchors to a metal oxide surface, resulting in robust anodes. Chapter 4 discusses a molecular nickel complex that is active in water oxidation catalysis, and depending on the pH and potential decomposes and deposits an active catalyst layer on the electrode. In Chapter 5 chemical oxidants are used to discover trends in molecular nickel complexes for water oxidation. In Chapter 6 a novel ligand framework is presented that forms iron complexes that result in high turnover numbers and frequencies in iron-catalyzed water oxidation. Overall, with this work we hope to encourage the development of first-row transition metal catalysts for water oxidation, with a focus on thorough mechanistic studies and exploring novel ligand frameworks.