The increasing need for carbon free energy has focused renewed attention on solar energy conversion. Although photovoltaic cells excel at directly converting of solar energy to electricity, they do not directly produce stored energy or fuels that account for more than 75% of current energy use. Direct photoelectrolysis of water has the advantage of converting solar energy directly to hydrogen, an ideal non-carbon and nonpolluting energy carrier, by replacing both a photovoltaic array and an electrolysis unit with one potentially inexpensive device. Unfortunately no materials are currently known to efficiently photoelectrolyze water that are, efficient, inexpensive and stable under illumination in electrolytes for many years. Nanostructured semiconducting metal oxides could potentially fulfill these requirements, making them the most promising materials for solar water photoelectrolysis, however no oxide semiconductor has yet been discovered with all the required properties. We have developed a simple, high-throughput combinatorial approach to prepare and screen many multi component metal oxides for water photoelectrolysis activity. The approach uses ink jet printing of overlapping patterns of soluble metal oxide precursors onto conductive glass substrates. Subsequent pyrolysis produces metal oxide phases that are screened for photoelectrolysis activity by measuring photocurrents produced by scanning a laser over the printed patterns in aqueous electrolytes. Several promising and unexpected compositions have been identified.

This book outlines many of the techniques involved in materials development and characterization for photoelectrochemical (PEC) – for example, proper metrics for describing material performance, how to assemble testing cells and prepare materials for assessment of their properties, and how to perform the experimental measurements needed to achieve reliable results towards better scientific understanding. For each technique, proper procedure, benefits, limitations, and data interpretation are discussed. Consolidating this information in a short, accessible, and easy to read reference guide will allow researchers to more rapidly immerse themselves into PEC research and also better compare their results against those of other researchers to better advance materials development. This book serves as a “how-to” guide for researchers engaged in or interested in engaging in the field of photoelectrochemical (PEC) water splitting. PEC water splitting is a rapidly growing field of research in which the goal is to develop materials which can absorb the energy from sunlight to drive electrochemical hydrogen production from the splitting of water. The substantial complexity in the scientific understanding and experimental protocols needed to sufficiently pursue accurate and reliable materials development means that a large need exists to consolidate and standardize the most common methods utilized by researchers in this field.

To better utilize solar energy for clean energy production, efforts are needed to overcome the natural diurnal variation and the diffuse nature of sunlight. Photoelectrochemical (PEC) hydrogen generation by water splitting is a promising approach to harvest solar energy. Hydrogen gas is a clean and high energy capacity fuel. However, the solar-to-hydrogen conversion efficiency is determined mainly by the properties of the materials employed as photoanodes. Improving the power-conversion efficiency of PEC water splitting requires the design of inexpensive and efficient photoanodes that have strong visible light absorption, fast charge separation, and lower charge recombination rate. In the present study, PEC characteristics of various semiconducting photoelectrodes such as TiO2, WO3 and CuWO4 were investigated. Due to the inherent wide gap, such metal oxides absorb only ultraviolet radiation. Since ultraviolet radiation only composes of 4% of the sun's spectrum, the wide band gap results in lower charge collection and efficiency. Thus to improve optical absorption and charge separation, it is necessary to modify the band gap with low band gap materials.The two approaches followed for modification of band gap are doping and sensitization. Here, TiO2 and WO3 based photoanodes were sensitized with ternary quantum dots, while doping was the primary method utilized to investigate the modification of the band gap of CuWO4. The first part of this dissertation reports the synthesis of ternary quantum dot - sensitized titania nanotube array photoelectrodes. Ternary quantum dots with varying band gaps and composition (MnCdSe, ZnCdSe and CdSSe) were tethered to the surface of TiO2 nanotubes using successive ionic layer adsorption and reaction (SILAR) technique. The stoichiometry of ternary quantum dots was estimated to beMn0.095Cd0.95Se, Zn0.16Cd0.84Se and CdS0.54Se0.46. The effect of varying number of sensitization cycles and annealing temperature on optical and photoelectrochemical properties of prepared photoanodes were studied. The absorption properties and surface morphology of the sensitized tubes was analyzed using UV-visible spectroscopy and scanning electron microscopy. The phase composition was determined using X-Ray diffraction and X-ray photoelectron spectroscopy techniques. Electrodes were also evaluated for their stability using inductively coupled plasma optical emission spectrometry. Results show that the sensitization of TiO2 nanotubes with MnCdSe (8.79 mA/cm2), ZnCdSe (12.70 mA/cm2) and CdSSe (15.58 mA/cm2) resulted in up to a 30 fold increase in photocurrent compared to unsensitized nanotubes (0.4 mA/cm2). In the second part, the application of WO3 as photoanode for water splitting was explored. The porous thin films of WO3 films were sensitized with ternary quantum dots (ZnCdSe) using the SILAR technique. The structural, surface morphological and optical properties of the sensitized WO3 thin films were studied. PEC characteristics of the sensitized films were found to be 120 fold increase (8.53 mA/cm2) in comparison to that of unmodified WO3 films (0.07 mA/cm2). In the last part of this dissertation, CuWO4 was investigated as the potential photoanode material. The band gap of CuWO4 was estimated using density functional theory (DFT) calculations. The band structure was obtained using the first-principles plane wave self-consistent field (pwscf) method and the effect of nickel dopant on the band gap and optical properties of CuWO4 was evaluated. Theoretical calculations showed that doping led to a decrease in band gap. The validity of the theoretical approach was evaluated by experimentally synthesizing Ni-doped CuWO4 electrodes. Experimental results showed that the band gap indeed decreases when CuWO4 was doped with Ni, and thus validated the DFT approach. Ternary quantum dots were found to increase the PEC activity of TiO2 and WO3 based photoelectrodes by 120 fold. In addition, a method of computing band gap of semiconductor using DFT modeling was developed and validated with experimental results.

Chemical energy storage by water splitting is a promising solution for the utilization of solar energy in numerous applications. Both efficient electrocatalysts and photocatalysts with a facile and scalable synthesis method are indispensable to achieve economic feasibility for water splitting. In the introductory chapter, a comprehensive review of electrochemical and photoelectrochemical (PEC) water splitting is provided and the fundamental concept of the PEC device design is described. Three different systems for water splitting were then explored in the following experimental chapters. In the second chapter, Manganese oxides (Mn3O4, Mn5O8 and Mn2O3) nanoparticles, with a range of specific surface area and crystal structures, were synthesized and compared. The nearly identical morphology of synthesized manganese oxide nanocrystals allows a systematic investigation on the relation between oxidation states and catalytic activities of different manganese oxide nanocrystals. Interesting discoveries regarding surface-specific turnover frequency, mole-specific turnover frequency and catalytic stability were demonstrated. Highly transparent and robust sub-monolayers of Co3O4 nano-islands were subsequently developed, which efficiently catalyse water oxidation with a comparable performance to noble metal-based catalysts. The potential of the Co3O4 nano-islands for photoelectrochemical water splitting has been demonstrated by incorporation of co-catalysts in GaN nanowire photoanodes. The Co3O4-GaN photoanodes reveal significantly reduced onset overpotentials, improved photoresponse and photostability compared to the bare GaN ones. In the last experimental chapter, we developed both physically- and chemically-induced morphology/structure tuning procedures, viz. capillary force-induced self-assembly and corrosion followed by regrowth, drastically increasing the water oxidation photocurrent density of nanostructured hematite photoanode. In addition to morphological changes, structural transformations were obtained by capillary force-induced self-assembly resulting in improved crystallinity of hematite with preferential orientation in the [110] direction. High conductivity of the hematite (001) basal planes contributes to the significantly enhanced photo-electrocatalytic activity. Subsequent dissolution and regrowth of hematite nanostructures further improved the performance, resulting in improved light absorption, more efficient charge separation and surface charge transfer processes.

The objective of this PhD is to develop the network of GaAs (core) / oxide (shell) nanowires for solar water splitting. The geometry of the GaAs nanowires was firstly optimized by adjusting different experimental parameters of the self-catalyzed growth of these nanowires by molecular beam epitaxy. We then systematically studied the surface oxidation of the GaAs nanowires and its negative effect on the growth of the shell. We have therefore developed a method called the arsenic (As) capping / decapping method that protects the facets of nanowires from the oxidation. A physico-chemical study has shown the beneficial effect of such a method on the growth of the shell. The growth of a SrTiO3 shell on GaAs nanowires was then performed. In-depth characterizations of SrTiO3 shell growth on GaAs nanowires were carried out. Most of the SrTiO3 perovskite structure was in epitaxial relationship with the GaAs crystalline lattice. The last part of this thesis concerns the application of such GaAs / oxide nanowire networks to PEC devices where the oxide serves as a passivation layer. The influence of the doping and the morphology of GaAs nanowires was first studied. The properties of GaAs / SrTiO3 and GaAs / TiO2 nanowire networks used as photoelectrodes in PEC devices are finally studied.

This book guides beginners in the areas of thin film preparation, characterization, and device making, while providing insight into these areas for experts. As chemically deposited metal oxides are currently gaining attention in development of devices such as solar cells, supercapacitors, batteries, sensors, etc., the book illustrates how the chemical deposition route is emerging as a relatively inexpensive, simple, and convenient solution for large area deposition. The advancement in the nanostructured materials for the development of devices is fully discussed.

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.