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

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

doi:10.1002/advs.202301876

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

Adv Sci (Weinh). 2023 Jul;10(19):e2301876. doi: 10.1002/advs.202301876. Epub 2023 Apr 25.

Authors

Takafumi Yamamoto¹, Shogo Kawaguchi², Taiki Kosuge¹, Akira Sugai¹, Naoki Tsunoda¹, Yu Kumagai^{1

3}, Kosuke Beppu⁴, Takuya Ohmi¹, Teppei Nagase¹, Kotaro Higashi², Kazuo Kato², Kiyofumi Nitta², Tomoya Uruga², Seiji Yamazoe^{5

6}, Fumiyasu Oba¹, Tsunehiro Tanaka^{6

7}, Masaki Azuma^{1

8

9}, Saburo Hosokawa^{6

10}

Affiliations

¹ Laboratory for Materials and Structures, Institute of Innovative Research, Tokyo Institute of Technology, Yokohama, 2268503, Japan.
² Japan Synchrotron Radiation Research Institute (JASRI), SPring-8, 1-1-1 Kouto, Sayo-gun, Hyogo, 6795198, Japan.
³ Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, 9808577, Japan.
⁴ Department of Applied Chemistry for Environment, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, 1-1 Minami-Osawa, Hachioji, Tokyo, 1920397, Japan.
⁵ Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, 1-1 Minami-Osawa, Hachioji, Tokyo, 1920397, Japan.
⁶ Elements Strategy Initiative for Catalysts & Batteries (ESICB), Kyoto University, Katsura, Nishikyo-ku, Kyoto, 6158245, Japan.
⁷ Department of Molecular Engineering, Graduate school of Engineering, Kyoto University, Nishikyo-ku, Kyoto, 6158510, Japan.
⁸ Living Systems Materialogy (LiSM) Research Group, International Research Frontiers Initiative (IRFI), Tokyo Institute of Technology, Yokohama, 2268501, Japan.
⁹ Kanagawa Institute of Industrial Science and Technology (KISTEC), 705-1 Shimoimaizumi, Ebina, Kanagawa, 2430435, Japan.
¹⁰ Faculty of Materials Science and Engineering, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto, 6068585, Japan.

Abstract

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 Sr₃ Fe₂ O_7- _δ (from δ ∼ 0.4 to δ = 1.0), which is promising for an environmental catalyst material is revealed. Pristine Sr₃ Fe₂ O_7- _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.

Keywords: oxygen storage material; perovskite oxide; synchrotron X-ray technique; time-resolved measurement; topochemical reaction.

Abstract

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