The hidden story in BaNiO3 to BaNiO2 transformation: adaptive structural series and NiO exsolution
BaNiO3 crystal to BaNiO2 crystal transformation is reported. Contrary to an intuitive topochemical reduction, a two step reaction was observed. In the first step, NiO exsolution occurs and intermediate Ba1+xNiO3 phases were obtained and isolated. A composite approach was used to solve the novel structure for x ∼ 1/6 with charge ordered Ni2+ and Ni4+. We argue that this NiO exsolution is responsible for the increased oxygen enhanced reactivity recently reported. Upon re-oxidation, oxygen-deficient mixed valent BaNi3/4+O3−x are obtained such that the full redox cycle is irreversible and goes through a diversity of structural and nickel valence adaptative oxides.
- This article is part of the themed collection: Perovskites