In situ encapsulation of iron(0) for solar thermochemical syngas production over iron-based perovskite material

Methane-to-syngas conversion plays an important role in industrial gas-to-liquid technologies, which is commercially fulfilled by energy-intensive reforming methods. Here we present a highly selective and durable iron-based La0.6Sr0.4Fe0.8Al0.2O3-delta oxygen carrier for syngas production via a solar-driven thermochemical process. It is found that a dynamic structural transformation between the perovskite phase and a Fe-0@oxides core-shell composite occurs during redox cycling. The oxide shell, acting like a micro-membrane, avoids direct contact between methane and fresh iron(0), and prevents coke deposition. This core-shell intermediate is regenerated to the original perovskite structure either in oxygen or more importantly in H2O-CO2 oxidant with simultaneous generation of another source of syngas. Doping with aluminium cations reduces the surface oxygen species, avoiding overoxidation of methane by decreasing oxygen vacancies in perovskite matrix. As a result, this material exhibits high stability with carbon monoxide selectivity above 95% and yielding an ideal syngas of H-2/CO ratio of 2/1.