Although photovoltaic cells have great potential for supplying carbon-free energy, they suffer from the lack of an efficient and cost-effective energy storage process that can supply energy for transportation and nighttime use. A direct way to convert solar energy into chemical fuels would solve this problem. Of several possible schemes, the photon-driven electrolysis of water to produce hydrogen and oxygen has been studied most. Photoelectrolysis of water can be achieved with either self-supported catalysts or with photoelectrochemical cells. This article will introduce the basic principles of solar water splitting and highlight recent developments with semiconductor light absorbers and co-catalysts. The role of combinatorial approaches in identifying new metal oxide visible light-absorbing semiconductors will be briefly described, and the potential of using nanomaterials for more efficient devices will be discussed. Separate articles in this special issue will focus on recent developments in water-splitting concepts.

Water splitting to form hydrogen and oxygen over a heterogeneous photocatalyst using solar energy is a promising process for clean and renewable hydrogen production. In recent years, numerous attempts have been made for the development of photocatalysts that work under visible light irradiation to efficiently utilize solar energy. This article reviews recent research progress in the development of visible light-driven photocatalysts, focusing on the refinement of oxynitride materials. They harvest visible photons (~450–700 nm) and work as stable photocatalysts for water reduction and oxidation under visible light. Oxynitrides with d0 electronic configuration can be successfully applied to a two-step water-splitting system, which can harvest a wide range of visible photons (~660 nm), in the presence of an iodate/iodide shuttle redox mediator. Also d10-type oxynitrides of GaN–ZnO and ZnGeN2–ZnO solid solutions can achieve functionality as photocatalysts for overall water-splitting under visible light without noticeable degradation.

Water splitting to produce H2 using sunlight is a form of artificial photosynthesis in that light energy is converted to chemical energy. As such, water splitting using powdered photocatalysts has attracted attention in the framework of energy and environmental issues. This article reviews z-scheme photocatalyst systems for water splitting under visible light irradiation, especially focused on the systems consisting of SrTiO3:Rh of a H2-evolving photocatalyst, and O2-evolving photocatalysts with and without electron mediators. These photocatalyst systems showed activities for water splitting into H2 and O2 in a stoichiometric amount under visible light irradiation and even under sunlight irradiation. The photocatalytic activity was sensitive to pH. The optimum pH was 2.4 when iron ions were used as electron mediators. Co-catalysts also affected the activity. The photodeposited Ru co-catalyst gave an excellent performance. The best performance achieved by the pH adjustment and the selection of a co-catalyst was obtained mainly by suppression of back reactions to form H2O from evolved H2 and O2.

Hydrogen generation using solar energy will require the development of efficient electrocatalysts for proton reduction. This article discusses the important role that proton movement plays in hydrogenase enzymes and potential devices for solar generation. Studies of hydrogenase enzymes provide many important design principles for the development of simpler molecular catalysts. These principles are illustrated with examples from the literature and from the authors’ laboratories. In particular, pendant bases incorporated in the second coordination sphere of catalytic molecules play a number of important roles that are crucial to efficient catalysis. These roles include acting as relays to move protons between the metal center and solution, promoting intra- and intermolecular proton transfer reactions, coupling proton and electron transfer reactions, assisting heterolytic cleavage of hydrogen, and stabilizing critical reaction intermediates. The importance of controlling proton movement on the molecular scale underscores the importance of a similar degree of control in devices designed for the solar production of hydrogen or any fuel generation process involving multiple electrons and protons.

This review focuses on recent developments in the study of hydrogen generation from water splitting using photoelectrochemical (PEC) cells based on metal oxide (MO) nanomaterials. The emphasis is on the unique properties of MO nanostructures and their advantages as well as limitations for PEC solar hydrogen generation. While abundant and stable, metal oxide nanomaterials tend to have weak visible light absorption that limits their use for solar energy conversion. In addition, MO nanomaterials tend to exhibit a high density of trap states or defect sites that limit their overall efficiency. Different strategies have been developed to enhance visible light absorption (e.g., doping, dye, or quantum dot sensitization and band structure engineering using composite structures) as well as to enhance transport by reducing the density of trap states via surface modification, improving crystallinity, or using 1D structures. In some cases, combining different strategies has led to strong synergistic effects. Recent studies point to the importance and promise of engineering electronic band structure for improving PEC performance of MO nanostructures for hydrogen generation and other potential applications.

This article is based on the Fred Kavli Distinguished Lectureship in Nanoscience presentation given by Harry Atwater (California Institute of Technology) on April 5, 2010 at the Materials Research Society Spring Meeting in San Francisco, CA. The Kavli Foundation supports scientific research, honors scientific achievement, and promotes public understanding of scientists and their work. Its particular focuses are astrophysics, nanoscience, and neuroscience.

Solar energy is currently enjoying substantial growth and investment, owing to worldwide sensitivity to energy security and climate change. Solar energy is an inexhaustible resource and is in abundant supply on all continents of the world. The power density of sunlight (~1000 W/m2) and the efficiency of photovoltaic devices (~10–25%) are high enough so that land use does not limit photovoltaic deployment at the terawatt scale. However solar photovoltaics are currently too expensive to achieve parity with other forms of electricity generation based on fossil fuels. This is largely due to the cost (and for some cases, the abundance) of materials used in photovoltaic modules and systems, and the cost of deploying in current form. This economic and social context has created the present situation where there is widespread interest in photovoltaic technology for power generation, but the cumulative installed world capacity for photovoltaics is <50 GW, and it appears to be very challenging for photovoltaics to play a very substantial role in large-scale (terawatt) electricity generation in the short term.