Abstract
The direct one-step CO2 and H2O splitting using an oxygen-transport membrane (OTM) reactor was investigated as a potentially ideal way to generate renewable fuels from concentrated solar energy. The solar-driven thermolysis of CO2 (or H2O) was promoted by in-situ oxygen removal across nonstoichiometric ceria-based membranes. A new solar membrane reactor integrating a tubular densified membrane made of either pure ceria or perovskite-coated ceria was designed and operated under high-flux concentrated solar radiation. A continuous flow of inert gas on the permeate side was used to create the required oxygen partial pressure gradient (driving force) and ensure continuous oxygen permeation via oxygen ion diffusion across the densified ceria membrane. The continuous OTM solar operation at high temperature was demonstrated through testing under various operating conditions. The CO and O2 production rates were sharply enhanced by increasing the operating temperature (up to 1550°C). The increase of CO2 concentration or oxidant gas flow rate also enhanced the process performance. Unprecedented fuel production rates (>0.07 μmol s−1 cm−2 at 1550°C) were achieved with a pure CO2 stream on the feed side and flowing Ar on the sweep side of the reactive ceria membrane. An original composite membrane integrating two different perovskite coatings on each side of the ceria membrane, with a sandwich-like structure, was designed and tested under concentrated sunlight. Thin layers of La0.5Sr0.5Mn0.9Mg0.1O3 on the inner side and Ca0.5Sr0.5MnO3 on the outer side were added to enhance oxygen ion transfer. With such a membrane configuration, a remarkable production of CO (>0.13 μmol s−1 cm−2) and oxygen (with CO:O2 ratio of 2) was obtained simultaneously, respectively on the inner and outer sides of the OTM. These results outperform the production rates achieved with the uncoated ceria membranes, and demonstrate the benefits of using composite membranes composed of a densified core material coated with (or sandwiched in between) redox active perovskite materials.