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.

The major goal of our research was to gain the ability in electrochemical synthesis to precisely control compositions and morphologies of various oxide-based polycrystalline photoelectrodes in order to establish the composition-morphology-photoelectrochemical property relationships while discovering highly efficient photoelectrode systems for use in solar energy conversion. Major achievements include: development of porous n-type BiVO4 photoanode for efficient and stable solar water oxidation; development of p-type CuFeO2 photocathode for solar hydrogen production; and junction studies on electrochemically fabricated p-n Cu2O homojunction solar cells for efficiency enhancement.

In this book, expert authors describe advanced solar photon conversion approaches that promise highly efficient photovoltaic and photoelectrochemical cells with sophisticated architectures on the one hand, and plastic photovoltaic coatings that are inexpensive enough to be disposable on the other. Their leitmotifs include light-induced exciton generation, junction architectures that lead to efficient exciton dissociation, and charge collection by percolation through mesoscale phases. Photocatalysis is closely related to photoelectrochemistry, and the fundamentals of both disciplines are covered in this volume./a

Photoelectrochemical Hydrogen Production describes the principles and materials challenges for the conversion of sunlight into hydrogen through water splitting at a semiconducting electrode. Readers will find an analysis of the solid state properties and materials requirements for semiconducting photo-electrodes, a detailed description of the semiconductor/electrolyte interface, in addition to the photo-electrochemical (PEC) cell. Experimental techniques to investigate both materials and PEC device performance are outlined, followed by an overview of the current state-of-the-art in PEC materials and devices, and combinatorial approaches towards the development of new materials. Finally, the economic and business perspectives of PEC devices are discussed, and promising future directions indicated. Photoelectrochemical Hydrogen Production is a one-stop resource for scientists, students and R&D practitioners starting in this field, providing both the theoretical background as well as useful practical information on photoelectrochemical measurement techniques. Experts in the field benefit from the chapters on current state-of-the-art materials/devices and future directions.

An electrically conducting polymer (polypyrrole) is employed in the stabilization of polycrystalline and single-crystal n-type Si electrodes in an electrochemical photovoltaic cell. The polymer adheres to the polycrystalline n-type Si more strongly than to the single-crystal material. The high capacitance of the polymer is an important factor in determining the ability of the polymer to stabilize the semiconductor. Polypyrrole in conjunction with a noble metal catalyst protects a tantalum electrode against an insulating oxide formation in an aqueous electrolyte under conditions of oxygen evolution.