CeTiO-A Promising Oxide for Solar Thermochemical Hydrogen Production.

A large entropy of reduction is crucial in achieving materials capable of high-efficiency solar thermochemical hydrogen (STCH) production through two-step thermochemical water splitting cycles. We have recently demonstrated that the onsite electronic entropy of reduction attains an extreme value of 4.26 at 1500 K in Ce → Ce redox reactions, which explains the high performance and uniqueness of CeO as an archetypal STCH material. However, ceria requires high temperatures ( > 1500 °C) to achieve a reasonable reduction extent because of its large reduction enthalpy, which is a major obstacle in practical applications. Therefore, new materials with a large entropy of reduction and lower reduction enthalpy are required. Here, we perform a systematic screening to search for Ce-based oxides which possess thermodynamics superior to CeO for STCH production. We first search the Inorganic Crystal Structure Database (ICSD) and literature for Ce-based oxides and subsequently use density functional theory to compute their reduction enthalpies (i.e., oxygen vacancy formation energies). We find that CeTiO with the brannerite structure is the most promising candidate for STCH because it possesses three essential characteristics of an STCH material: (i) a smaller reduction enthalpy compared to ceria yet large enough to split water, (ii) a high thermal stability, as reported experimentally, and (iii) a large entropy of reduction associated with Ce → Ce redox. Our proposed design strategy suggests that further exploration of Ce oxides for STCH production is warranted.