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The solar-driven transformation of water and carbon dioxide into valuable chemicals offers a sustainable route to bypass the use of fossil fuels. This can be achieved using molecular catalysts immobilised on semiconductor surfaces. Hybrid photocathodes, which are responsible for fuel-forming reactions in these devices, have drawn knowledge from multiple fields of research to identify and overcome performance-limiting components. This chapter discusses advances in dye-sensitised and visible-light-absorbing semiconductor systems by first presenting an overview of semiconductor electrochemistry and molecular catalysis. Specific examples of functional photocathodes are then used to highlight how innovative approaches can enhance photoelectrochemical performance, providing guidelines for future research.

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