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.

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.

Photoelectrocatalysis: Fundamentals and Applications presents an in-depth review of the topic for students and researchersworking on photoelectrocatalysis-related subjects from pure chemistry to materials and environmental chemistry inorder to propose applications and new perspectives. The main advantage of a photoelectrocatalytic process is the mildexperimental conditions under which the reactions are carried out, which are often possible at atmospheric pressure androom temperature using cheap and nontoxic solvents (e.g., water), oxidants (e.g., O2 from the air), catalytic materials (e.g.,TiO2 on Ti layer), and the potential exploitation of solar light. This book presents the fundamentals and the applications of photoelectrocatalysis, such as hydrogen production fromwater splitting, the remediation of harmful compounds, and CO2 reduction. Photoelectrocatalytic reactors and lightsources, in addition to kinetic aspects, are presented along with an exploration of the relationship between photocatalysisand electrocatalysis. In addition, photocorrosion issues and the application of selective photoelectrocatalytic organictransformations, which is now a growing field of research, are also reported. Finally, the advantages/disadvantages andfuture perspectives of photoelectrocatalysis are highlighted through the possibility of working at a pilot/industrial scale inenvironmentally friendly conditions. Presents the fundamentals of photoelectrocatalysis Outlines photoelectrocatalytic green chemistry Reviews photoelectrocatalytic remediation of harmful compounds, hydrogen production, and CO2 reduction Includes photocorrosion, photoelectrocatalytic reactors, and modeling along with kinetic aspects

Among several pathways to harvest solar energy, solar water splitting is one of the most efficient methods to convert solar light to hydrogen, which is a clean and easy to store chemical that has the potential to be used as a fuel source. Solar water splitting can be achieved primarily by photoelectrochemical cells (PECs), which utilize semiconductors as photoelectrodes for the water splitting reaction. Photoelectrodes play the crucial role of generating hydrogen but, to date, very few photoelectrodes have been developed that can produce hydrogen in a stable and efficient manner. Thus, development and modification of efficient, stable photoelectrodes are highly desirable to improve performance of solar water splitting PECs. This dissertation demonstrates the development of semiconductors as photoelectrodes and their modifications to advance solar energy conversion performance by newly established electrochemical synthetic routes. To improve the photoelectrochemical performance of photoelectrodes, various strategies were introduced, such as, morphology control, extrinsic doping, and the integration of catalysts. After successfully demonstrating the electrochemical synthesis of photoelectrodes, photoelectrochemical and electrochemical properties of electrodeposited photoelectrodes in PECs are discussed. The chapters can be categorized into three major themes. The first theme is the preparation of Bi-based photoanodes for the water oxidation reaction. Chapter 2 presents a study of Mo-doping into the BiVO4 photoanode to enhance charge separation properties. After Mo-doping was achieved successfully, a FeOOH oxygen evoltuion catalyst was integrated into the Mo-doped BiVO4 photoanode to increase the water oxidation performance. Chapter 3 introduces another electrochemical synthesis method to control the morphology of Bi-based oxide photoanode materials. The second theme of this dissertation is the preparation of photocathode materials for the water reduction reaction. Chapter 4 discusses the development of the CuBi2O4 photocathode, which is modified by Ag-doping, morphology control, and catalyst integration to improve the overall cell performance. In chapter 5, both n-InP and p-InP are prepared by an electrochemical route to demonstrate the plausibility that electrochemical routes can be utilized to prepare InP photoelectrodes. The final theme is the construction of photovoltaic devices. In chapter 6, all-electrodeposited ZnO/Cu2O and Al-doped ZnO/Cu2O solar cells are fabricated and their solar cell performances are studied.

This book review series presents current trends in modern biotechnology. The aim is to cover all aspects of this interdisciplinary technology where knowledge, methods and expertise are required from chemistry, biochemistry, microbiology, genetics, chemical engineering and computer science. Volumes are organized topically and provide a comprehensive discussion of developments in the respective field over the past 3-5 years. The series also discusses new discoveries and applications. Special volumes are dedicated to selected topics which focus on new biotechnological products and new processes for their synthesis and purification. In general, special volumes are edited by well-known guest editors. The series editor and publisher will however always be pleased to receive suggestions and supplementary information. Manuscripts are accepted in English.

Nowadays clean and renewable energy supply is one of the biggest challenges for the mankind. Hydrogen is often proposed as a prospective fuel of the future, but there are numerous scientific and technological problems to be solved on the way to the hydrogen economy. One of them is hydrogen production. The most efficient way of hydrogen production would be direct water splitting using solar energy. Photoelectrode materials for solar water splitting cells must fulfill a number of requirements: an appropriate band gap, band edge positions, high specific surface area, long term chemical and mechanical stability, low cost of fabrication. In this work, porous thin film electrodes for photoelectochemical solar water splitting were developed by the dealloying approach. The search for materials with optimal physical and photoelectrochemical properties inevitably involves fabrication and characterization of a large number of samples. In order to accelerate this search, combinatorial and high-throughput methods were used for fabrication and investigation of the thin film materials libraries.