Solar Energy for Fuels

Solar energy provides by far the greatest potential for energy generation among all forms of renewable energy. Yet, just as for any form of energy conversion, it is subject to physical limits. Here we review the physical limits that determine how much energy can potentially be generated out of sunlight using a combination of thermodynamics and observed climatic variables. We first explain how the first and second law of thermodynamics constrain energy conversions and thereby the generation of renewable energy, and how this applies to the conversions of solar radiation within the Earth system. These limits are applied to the conversion of direct and diffuse solar radiation – which relates to concentrated solar power (CSP) and photovoltaic (PV) technologies as well as biomass production or any other photochemical conversion – as well as solar radiative heating, which generates atmospheric motion and thus relates to wind power technologies. When these conversion limits are applied to observed data sets of solar radiation at the land surface, it is estimated that direct concentrated solar power has a potential on land of up to 11.6 PW (1 PW = 10¹⁵ W), whereas photovoltaic power has a potential of up to 16.3 PW. Both biomass and wind power operate at much lower efficiencies, so their potentials of about 0.3 and 0.1 PW are much lower. These estimates are considerably lower than the incoming flux of solar radiation of 175 PW. When compared to a 2012 primary energy demand of 17 TW, the most direct uses of solar radiation, e.g., by CSP or PV, have thus by far the greatest potential to yield renewable energy requiring the least space to satisfy the human energy demand. Further conversions into solar-based fuels would be reduced by further losses which would lower these potentials. The substantially greater potential of solar-based renewable energy compared to other forms of renewable energy simply reflects much fewer and lower unavoidable conversion losses when solar radiation is directly converted into renewable energy.

Nature relies on a unique and intricate biochemical setup to achieve sunlight-driven water splitting. Combined experimental and computational efforts have produced significant insights into the structural and functional principles governing the operation of the water-oxidizing enzyme Photosystem II in general, and of the oxygen-evolving manganese–calcium cluster at its active site in particular. Here we review the most important aspects of biological water oxidation, emphasizing current knowledge on the organization of the enzyme, the geometric and electronic structure of the catalyst, and the role of calcium and chloride cofactors. The combination of recent experimental work on the identification of possible substrate sites with computational modeling have considerably limited the possible mechanistic pathways for the critical O–O bond formation step. Taken together, the key features and principles of natural photosynthesis may serve as inspiration for the design, development, and implementation of artificial systems.

The catalytic oxidation of water to molecular oxygen is a key process for the production of solar fuels. Inspired by the biological manganese-based active site for this reaction in the enzyme Photosystem II, researchers have made impressive progress in the last decades regarding the development of synthetic manganese catalysts for water oxidation. For this, it has been especially fruitful to explore the many different types of known manganese oxides MnO _x .

This chapter first offers an overview of the structural, thermodynamic, and mechanistic aspects of water-oxidation catalysis by MnO _x . The different test systems used for catalytic studies are then presented together with general reactivity trends. As a result, it has been possible to identify layered, mixed Mn ^III/IV -oxides as an especially promising class of bio-inspired catalysts and an attempt is made to give structure-based reasons for the good performances of these materials.

In the outlook, the challenges of catalyst screenings (and hence the identification of a “best MnO _x catalyst”) are discussed. There is a great variety of reaction conditions which might be relevant for the application of manganese oxide catalysts in technological solar fuel-producing devices, and thus catalyst improvements are currently still addressing a very large parameter space. Nonetheless, detailed knowledge about the biological catalyst and a solid experimental basis concerning the syntheses and water-oxidation reactivities of MnO _x materials have been established in the last decade and thus this research field is well positioned to make important contributions to solar fuel research in the future.

Solar energy conversion is essential to address the gap between energy production and increasing demand. Large scale energy generation from solar energy can only be achieved through equally large scale collection of the solar spectrum. Overall water splitting using heterogeneous photocatalysts with a single semiconductor enables the direct generation of H₂ from photoreactors and is one of the most economical technologies for large-scale production of solar fuels. Efficient photocatalyst materials are essential to make this process feasible for future technologies. To achieve efficient photocatalysis for overall water splitting, all of the parameters involved at different time scales should be improved because the overall efficiency is obtained by the multiplication of all these fundamental efficiencies. Accumulation of knowledge ranging from solid-state physics to electrochemistry and a multidisciplinary approach to conduct various measurements are inevitable to be able to understand photocatalysis fully and to improve its efficiency.

From a conceptual standpoint, the water photoelectrolysis reaction is the simplest way to convert solar energy into fuel. It is widely believed that nanostructured photocatalysts can improve the efficiency of the process and lower the costs. Indeed, nanostructured light absorbers have several advantages over traditional materials. This includes shorter charge transport pathways and larger redox active surface areas. It is also possible to adjust the energetics of small particles via the quantum size effect or with adsorbed ions. At the same time, nanostructured absorbers have significant disadvantages over conventional ones. The larger surface area promotes defect recombination and reduces the photovoltage that can be drawn from the absorber. The smaller size of the particles also makes electron–hole separation more difficult to achieve. This chapter discusses these issues using selected examples from the literature and from the laboratory of the author.

Combining different light-absorbing materials for the formation of semiconductor heterojunctions is a very effective strategy for preparing highly active photocatalyst and photoelectrochemical systems. Moreover, the combination of solid state semiconductors with polymers or molecular absorbers expands the possible combinations of materials to alter light absorption and optimize charge carrier separation. In this chapter, different strategies to prepare such composites are presented, highlighting the necessity of intimate interfacial contact for optimum charge carrier transfer. Moreover, the most recent developments and improvements in the formation of heterojunctions and composite photocatalyst systems based on semiconductor solids are presented.

The contemporary demand to generate fuels from solar energy has stimulated intense effort to develop water splitting catalysts that can be coupled to light-absorbing materials. Cobalt oxido catalyst (Co-OECs) films deposited from buffered Co^II solutions have emerged as arguably the most studied class of heterogeneous oxygen evolution catalysts. The interest in these materials stems from their formation by self-assembly, their self-healing properties, and their promising catalytic activity under a variety of conditions. The structure and function of these catalysts are reviewed here together with studies of molecular Co-O cluster compounds, which have proven invaluable in elucidating the chemistry of the Co-OECs.

The utilization of localized surface plasmon resonance (LSPR) from plasmonic noble metals in combination with semiconductors promises great improvements for visible light-driven photocatalysis, in particular for energy conversion. This review summarizes the basic principles of plasmonic photocatalysis, giving a comprehensive overview about the proposed mechanisms for enhancing the performance of photocatalytically active semiconductors with plasmonic devices and their applications for surface plasmon-assisted solar energy conversion. The main focus is on gold and, to a lesser extent, silver nanoparticles in combination with titania as semiconductor and their usage as active plasmonic photocatalysts. Recent advances in water splitting, hydrogen generation with sacrificial organic compounds, and CO₂ reduction to hydrocarbons for solar fuel production are highlighted. Finally, further improvements for plasmonic photocatalysts, regarding performance, stability, and economic feasibility, are discussed for surface plasmon-assisted solar energy conversion.

In situ and operando techniques can play important roles in the development of better performing photoelectrodes, photocatalysts, and electrocatalysts by helping to elucidate crucial intermediates and mechanistic steps. The development of high throughput screening methods has also accelerated the evaluation of relevant photoelectrochemical and electrochemical properties for new solar fuel materials. In this chapter, several in situ and high throughput characterization tools are discussed in detail along with their impact on our understanding of solar fuel materials.