The Hidden Hydroxide in BaNiO3 Single Crystals Grown from a KOH Flux

Hexagonal oxide perovskites with one-dimensional chains of face-sharing MO6 octahedra are of enduring interest. Specifically, the hexagonal perovskite BaNiO3, prepared via non-ceramic approaches, acts as a highly functional catalyst for the oxygen-evolution reaction (OER) in alkaline media, with numerous studies focusing on this behavior, while its fundamental structural and physical properties have been somewhat overlooked. The current work is intiated by the observation of contrasting magnetic properties of BaNiO3 synthesized via KOH flux growth and high O2 pressure ceramic synthesis. To shed light on this difference, we have performed a series of rigorous analyses and found that the KOH flux-grown crystals made in open-air are actually a wet form of BaNiO3 that can be dried upon annealing in O2 flow but will then slowly degrade if stored under a condition where the O2 partial pressure is not high enough. Therefore, the present work not only provides insightful information to unveil a previously unknown aspect of the OER catalyst BaNiO3, but also rings a bell that the hidden hydroxide principle described here may also be applied to other hexagonal perovskite oxides prepared in wet conditions.