Finding alternatives to fossil-based fuels is of the utmost importance because of the harmful effects of these fuels on the environment and public health. Solar energy is a promising alternative for renewable energy generation because it is both sustainable and environmentally friendly. Through photoelectrochemical water splitting, hydrogen can be directly generated from sunlight to produce a renewable chemical fuel. Photoelectrodes are the key components of photoelectrochemical water splitting cells. For optimal performance with high durability, photoelectrodes must be coupled with electrocatalysts and/or protective layers to form multicomponent photoelectrode systems. To form optimal systems, it is critical to understand and control the individual process that occur at the interfaces between the components. The work presented herein first shows a new electrochemical synthesis route to produce a TiO2 protective layer to build a robust BiVO4/TiO2 photoelectrode system that is stable in alkaline media. The successful fabrication of the BiVO4/TiO2 electrode allowed for systematic studies to conclude that the rate of photocorrosion of BiVO4 increases drastically when BiVO4 is chemically unstable. Studies on the BiVO4/electrolyte interface were also conducted by designing epitaxially grown BiVO4 films with two distinct well-defined surfaces. BiVO4 with a Bi-rich surface showed an improved performance for photoelectrochemical water oxidation compared with the V-rich surface, indicating that the Bi-rich surface resulted in a more favorable BiVO4/electrolyte interface. Studies were also conducted on the electrochemical oxidation of metal-catechol complexes as a new synthesis strategy to produce a phase-pure, high-quality Fe2TiO5 photoanode. Lastly, a Bi2S3 photoanode was prepared through an anion exchange reaction using a BiVO4 electrode as a precursor electrode. A WS3-x layer was then electrochemically deposited on the Bi2S3 electrode as a protective layer for the first time on a sulfide-based photoanode. Enhanced stability for photoelectrochemical H2S splitting was achieved by the Bi2S3/WS3-x electrode. Overall, this dissertation presents new interesting (electro)chemical synthesis methods for a variety of metal oxide- and sulfide-based semiconductor electrodes and protective layers. Insights presented here on the photoelectrode/protective layer and photoelectrode/electrolyte interfaces provide a foundation to better understand the numerous interfaces present in multicomponent photoelectrode systems.

The development of renewable and environmentally benign methods to replace fossil fuel extraction for chemical and fuel production is vital to reduce CO2 emissions and limit the effects of climate change. Solar energy is widely available as a renewable clean energy source. The use of photoelectrochemistry to harness solar energy for chemical and fuel production can decrease society's dependence on fossil fuels and reduce CO2 emissions. The key component of a photoelectrochemical cell is the semiconductor photoelectrode. Bi-based oxide materials have been shown to be effective photoelectrodes due to their small band gaps and excellent charge separation efficiencies. Current areas of research into photoelectrodes include new material discovery, optimization of already known materials, and investigation of new reactions to perform photoelectrochemically. The work herein presents research into all of these areas using Bi-based and other metal oxide materials. First, a combined experimental and computational investigation of the interface between BiVO4 and FeOOH was conducted to improve our understanding of charge transfer between a photoabsorber and catalyst layer. It was discovered that varying the surface of BiVO4 between stoichiometric and Bi-rich affects the deposition of the FeOOH layer, and therefore the energetics at the interface, leading to significantly improved performance for the Bi-rich film. Alcohol oxidation on a BiVO4 photoanode was also investigated using the renewable feedstock chemical glycerol as a method for renewable chemical production. It was discovered that BiVO4 has a unique ability to promote a C-C coupling reaction that generates glycolaldehyde as the primary product, which has never been reported. SrBiO3 was also discovered as a photoelectrode material and synthesized as a thin film under ambient pressure for the first time. Investigation of its material properties and photoelectrochemical performance found SrBiO3 to be a promising photocathode material. Finally, a new electrochemical synthesis method was developed for the materials Fe2O3, CuO, CuFe2O4, and CuFeO2 utilizing the oxidation of catechol-metal complexes to deposit the desired metals. This method allowed for controlled ratios of Cu and Fe to be deposited and resulted in high surface area films that are favorable for use as photoelectrodes.

An up-to-date reference reflecting the significant advances and important breakthroughs made in this emerging discipline over the last decade. As such, the book provides an overview of the latest developments and future trends in the field, focusing on such applications as the development of potentially active organometallic drugs against incurable diseases, as well as in such areas as catalysis, energy, analytical chemistry, and imaging. The renowned editor, who established the term "bioorganometallics", and his international team of experts have put together a valuable resource for researchers in organometallic, inorganic, medicinal, and biochemistry.