Drop-in fuels from sunlight and air.

Aviation and shipping currently contribute approximately 8% of total anthropogenic CO2 emissions, with growth in tourism and global trade projected to increase this contribution further1-3. Carbon-neutral transportation is feasible with electric motors powered by rechargeable batteries, but is challenging, if not impossible, for long-haul commercial travel, particularly air travel4. A promising solution are drop-in fuels (synthetic alternatives for petroleum-derived liquid hydrocarbon fuels such as kerosene, gasoline or diesel) made from H2O and CO2 by solar-driven processes5-7. Among the many possible approaches, the thermochemical path using concentrated solar radiation as the source of high-temperature process heat offers potentially high production rates and efficiencies8, and can deliver truly carbon-neutral fuels if the required CO2 is obtained directly from atmospheric air9. If H2O is also extracted from air10, feedstock sourcing and fuel production can be colocated in desert regions with high solar irradiation and limited access to water resources. While individual steps of such a scheme have been implemented, here we demonstrate the operation of the entire thermochemical solar fuel production chain, from H2O and CO2 captured directly from ambient air to the synthesis of drop-in transportation fuels (for example, methanol and kerosene), with a modular 5 kWthermal pilot-scale solar system operated under field conditions. We further identify the research and development efforts and discuss the economic viability and policies required to bring these solar fuels to market.

Thermochemical CO2 splitting via redox cycling of ceria reticulated foam structures with dual-scale porosities.

Efficient heat transfer of concentrated solar energy and rapid chemical kinetics are desired characteristics of solar thermochemical redox cycles for splitting CO2. We have fabricated reticulated porous ceramic (foam-type) structures made of ceria with dual-scale porosity in the millimeter and micrometer ranges. The larger void size range, with dmean = 2.5 mm and porosity = 0.76-0.82, enables volumetric absorption of concentrated solar radiation for efficient heat transfer to the reaction site during endothermic reduction, while the smaller void size range within the struts, with dmean = 10 µm and strut porosity = 0-0.44, increases the specific surface area for enhanced reaction kinetics during exothermic oxidation with CO2. Characterization is performed via mercury intrusion porosimetry, scanning electron microscopy, and thermogravimetric analysis (TGA). Samples are thermally reduced at 1773 K and subsequently oxidized with CO2 at temperatures in the range 873-1273 K. On average, CO production rates are ten times higher for samples with 0.44 strut porosity than for samples with non-porous struts. The oxidation rate scales with specific surface area and the apparent activation energy ranges from 90 to 135.7 kJ mol(-1). Twenty consecutive redox cycles exhibited stable CO production yield per cycle. Testing of the dual-scale RPC in a solar cavity-receiver exposed to high-flux thermal radiation (3.8 kW radiative power at 3015 suns) corroborated the superior performance observed in the TGA, yielding a shorter cycle time and a mean solar-to-fuel energy conversion efficiency of 1.72%.

High-flux solar-driven thermochemical dissociation of CO2 and H2O using nonstoichiometric ceria.

Because solar energy is available in large excess relative to current rates of energy consumption, effective conversion of this renewable yet intermittent resource into a transportable and dispatchable chemical fuel may ensure the goal of a sustainable energy future. However, low conversion efficiencies, particularly with CO(2) reduction, as well as utilization of precious materials have limited the practical generation of solar fuels. By using a solar cavity-receiver reactor, we combined the oxygen uptake and release capacity of cerium oxide and facile catalysis at elevated temperatures to thermochemically dissociate CO(2) and H(2)O, yielding CO and H(2), respectively. Stable and rapid generation of fuel was demonstrated over 500 cycles. Solar-to-fuel efficiencies of 0.7 to 0.8% were achieved and shown to be largely limited by the system scale and design rather than by chemistry.