Iron precipitated onto ceria-zirconia nanoparticle mixtures for the production of hydrogen via two-step thermochemical water splitting

Several novel materials were synthesized by precipitating iron oxide (using the previously optimized 10% Fe loading by weight) onto mixtures of nanoparticle zirconia and ceria to investigate the effects of adding CeO2 to FeOx/ZrO2 materials in the thermochemical water splitting reaction. At water splitting temperatures of 1000 °C (after thermal reduction at 1450 °C), the stability of the CeO2-containing materials was lower than for the FeOx/ZrO2 material, and there was no advantage to adding CeO2 to the FeOx/ZrO2 material. However, when operating at a water splitting (WS) temperature of 1200 °C, the stability increased and the hydrogen production was significantly higher over most materials compared with a water splitting temperature of 1000 °C. At a WS temperature of 1200 °C the FeOx/Zr75Ce25O2 (75% Zr75O2 and 25% CeO2 by weight) and FeOx/Zr50Ce50O2 materials performed slightly better than the FeOx/ZrO2 material, and X-ray photoelectron spectroscopy data revealed that the surface concertation of iron is less important compared with water splitting at 1000 °C. The temperature programmed reduction data indicated that the FeOx-CeO2 interactions were weaker compared with FeOx-ZrO2 interactions, since the FeOx reduction occurred at lower temperatures for the CeO2-containing materials. The weaker interactions can explain why the stability was lower for the materials containing CeO2 (sintering of FeOx was likely more pronounced) The X-ray diffraction data revealed that ZrO2-CeO2 solid solutions formed after activation at 1450 °C and lattice volume calculations indicated that iron did incorporate into the ZrO2-CeO2 matrices. More incorporation was observed after water-splitting at 1200 °C compared with a lower temperature (1000 °C), and likely explains why the materials were more stable during water-splitting at 1200 °C.