Journal Article

Emergence of Dynamically‐Disordered Phases During Fast Oxygen Deintercalation Reaction of Layered Perovskite

Kawaguchi, Shogo, Hosokawa, Saburo, Ohmi, Takuya, Nagase, Teppei, Oba, Fumiyasu, Sugai, Akira, Kumagai, Yu, Nitta, Kiyofumi, Kato, Kazuo, Tanaka, Tsunehiro, Tsunoda, Naoki, Kosuge, Taiki, Yamazoe, Seiji, Uruga, Tomoya, Azuma, Masaki, Higashi, Kotaro, Beppu, Kosuke, Yamamoto, Takafumi

2023

Overview

Determination of a reaction pathway is an important issue for the optimization of reactions. However, reactions in solid‐state compounds have remained poorly understood because of their complexity and technical limitations. Here, using state‐of‐the‐art high‐speed time‐resolved synchrotron X‐ray techniques, the topochemical solid‐gas reduction mechanisms in layered perovskite Sr3Fe2O7−δ (from δ ∼ 0.4 to δ = 1.0), which is promising for an environmental catalyst material is revealed. Pristine Sr3Fe2O7−δ shows a gradual single‐phase structural evolution during reduction, indicating that the reaction continuously proceeds through thermodynamically stable phases. In contrast, a nonequilibrium dynamically‐disordered phase emerges a few seconds before a first‐order transition during the reduction of a Pd‐loaded sample. This drastic change in the reaction pathway can be explained by a change in the rate‐determining step. The synchrotron X‐ray technique can be applied to various solid‐gas reactions and provides an opportunity for gaining a better understanding and optimizing reactions in solid‐state compounds. The topochemical solid‐gas reduction mechanisms from Sr3Fe2O7−δ to Sr3Fe2O6 is investigated by high‐speed time‐resolved synchrotron X‐ray techniques. The reaction pathways drastically change by Pd‐loading, and a dynamically‐disordered phase emerges a few seconds during the reduction of the Pd‐loaded Sr3Fe2O7−δ. This synchrotron X‐ray technique will provide an opportunity for gaining a better understanding and optimizing various solid‐gas reactions.

• Publisher: John Wiley & Sons, Inc,John Wiley and Sons Inc,Wiley
• Subject: Data collection / Evolution / Gas absorption / Measurement techniques / Nanoparticles / NMR / Nuclear magnetic resonance / oxygen storage material / perovskite oxide / Phosphates / synchrotron X‐ray technique / Temperature / time‐resolved measurement / topochemical reaction / X-rays