Hydrogen production by thermochemical water splitting with La0.8Al0.2MeO3-δ (Me= Fe, Co, Ni and Cu) perovskites prepared under controlled pH, A. Pérez, M. Orfila, M. Linares, R. Sanz, J. Marugán, R. Molina, J. A. Botas, Catalysis Today, 390, 22-33, 2022, Online version,  https://doi.org/10.1016/j.cattod.2021.12.014


Aluminum based perovskites, La0.8Al0.2MeO3-δ (Me = Co, Ni, Fe, Cu), were synthesized following the Pechini method at different pHs and evaluated for hydrogen production by water splitting in a two-step thermochemical cycle. The pH of the synthesis medium showed a critical influence in the redox properties of the aluminum-based perovskites during the thermochemical cycle. Both the thermal reduction and the hydrolysis step produce irreversible changes in the crystalline structure of La0.8Al0.2MeO3-δ perovskites prepared at acid pH, avoiding the cyclability of the material and a stable production of hydrogen during consecutive cycles. However, these changes are not observed when the perovskites were synthesized at basic pH and operated at isothermal conditions at 800 ºC. In this case, the materials keep the crystalline structure leading to stable hydrogen production during consecutive cycles. Among all the studied materials, the nickel-based La0.8Al0.2NiO3-δ perovskites exhibited the best hydrogen productivity per cycle, 4.4 cm3 STP /gmaterial·cycle (Standard Temperature and Pressure conditions), which is a remarkable result considering that the thermochemical water splitting is conducted under isothermal conditions at just 800 ºC. Moreover, this result is accompanied with a good performance of the perovskite in terms of solar to fuel efficiency (being 0.46 the ratio between the potential energy recovery from the produced hydrogen and the solar heat required for its production), comparable or even higher than values reported in the literature for other metal oxides. These results confirm the La0.8Al0.2NiO3-δ perovskite as an auspicious material for a full-scale H2 production from water splitting by solar-driven thermochemical cycles at low temperatures.