There is a critical need for basic research in solar fuel generation by splitting water into hydrogen and oxygen, and reducing carbon dioxide into energy-rich fuels. Hybrid photocatalysts, consisting of molecular catalysts grafted onto semiconductor surfaces, have emerged as promising systems for solar-to-fuel conversion. This project aims to identify structural features of covalent linkages between molecular catalysts and semiconductor surfaces that are key to achieving efficient solar fuel generation. The PIs at the University of New Hampshire will collaborate with Dr. Tijana Rajh of Argonne National Laboratory to investigate how bend angles and flexibility of the covalent linkages affect photochemical reduction of carbon dioxide. A modular approach has been designed to allow the synthesis of a variety of covalent linkages for use in grafting coordination complexes of cobalt and copper on nitrogen-doped tantalum oxide surfaces. The research objectives will be achieved by studying the synthesized hybrid photocatalysts using advanced spectroscopic techniques, including infrared spectroscopy and electron paramagnetic resonance spectroscopy. This research effort will contribute fundamental understanding to advance capabilities to design artificial photosynthetic assemblies based on earth-abundant elements for efficient solar fuel generation.