Metal oxides are reviewed as catalysts to convert H 2 O and CO 2 to fuels using solar energy. For photochemical conversion, TiO 2 has been found to be the most stable and useful oxide material, but it is currently limited by its large bandgap and a mismatch between its conduction band and the redox couples for water splitting and CO 2 reduction. A theoretical framework has been utilized to understand the basic thermodynamics and energetics in photochemical energy conversion systems. This is applied to model systems comprised of Ag 2 O and AgCl to examine why the former reacts thermochemically in air, while the latter reacts photochemically. For thermochemical conversion, zinc-, ceria-, and ferrite-based redox cycles are examined and examples of high-temperature solar reactors driven by concentrated solar radiation are presented. For CO 2 splitting, theoretical solar-to-fuel energy conversion efficiencies can be up to 26.8% for photochemical systems, and can exceed 30% for thermochemical systems, provided that sensible heat is recovered between the redox steps.
■ INTRODUCTIONThe conversion of solar energy into useful forms has reached a critical stage where large-scale industrial applications are allowing it to make significant and promising contributions to our present and future energy needs. In this review, we present some basic concepts and survey a few of the recent developments in the conversion of solar energy into fuel. Several types of systems are possible, some of which are based on thermochemistry, 1 while others are based on photochemistry. 2 Photovoltaic cells and modules 3−7 have also emerged as an important part of the energy mixture of many countries, but they will not be fully examined in this review. The storage of solar energy has recently been reported in this journal. 8 The first section of this review focuses on the photochemical production of fuels and includes a generalized framework that can be used to understand the energetics and mechanism of both photovoltaic (PV) solar cells, as well as solar photochemistry using semiconductor materials. 9−12 This framework will be applied to a consideration of Ag 2 O, which is a model metal oxide system that, in air, seems to react thermochemically but not photochemically. The second half of this review focuses on the solar thermochemical splitting of H 2 O and CO 2 via metal oxide redox cycles. A comparison between metal oxide and solar electrolysis fuel-forming systems will also be presented.
■ DISCUSSIONPhotochemistry and Quantum Solar Converters. Two forms of solar energy conversion are considered. One is thermal conversion, where work can be extracted after sunlight is absorbed as thermal energy, and the other is quantum conversion, where the work output can be taken directly from the light absorber. In a thermal system, solar radiation is absorbed as heat, preferably at some high temperature, which, in turn, is used to drive a heat engine. In a quantum system, a fixed number of photons yield a fixed number of energy quanta, such as excited elect...