As a virtually inexhaustible source, solar energy plays a major role in future global energy scenarios. Solar-driven water splitting via dye-sensitized photoelectrochemical (DS-PEC) devices is a... Show moreAs a virtually inexhaustible source, solar energy plays a major role in future global energy scenarios. Solar-driven water splitting via dye-sensitized photoelectrochemical (DS-PEC) devices is a scalable, affordable and sustainable technology of great potential for direct conversion of solar energy into storable chemical fuels to produce clean, cost-efficient and environmentally friendly H2 or CO2-derived fuels and thus to contribute to the transformation of a sustainable society from the blueprint to reality. Proton-coupled electron transfer (PCET) plays a crucial role in a wide range of biological and chemical reactions concerning energy conversion processes, such as natural and artificial photosynthesis. Given that the overall catalytic water oxidation consists of four consecutive PCET steps, sequential or concerted, it is therefore of fundamental significance to unveil the intrinsic catalytic mechanism as well as the factors determining the PCET rate and thus to find strategies to facilitate the catalytic water oxidation. Computational tools provide a powerful and essential technique for the understanding and engineering of efficient DS-PEC devices for water splitting. This thesis provides an in-depth understanding of the catalytic mechanisms for the water oxidation half-reaction in catalyst-dye supramolecular complexes and rational strategies to facilitate the involved catalytic reactions. Show less
