In situ atomic-resolution imaging of water vapor-driven multistep oxidation dynamics in strontium cobaltite.

Yang, Zhenzhong; Qu, Ke; Zhao, Yifeng; Wang, Le; Kovarik, Libor; Sushko, Peter V; Lyu, Yingjie; Zhang, Jianbing et al. · Sci Adv · 2025

basic_science · Level V

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Abstract

Understanding how water vapor interacts with transition metal oxides (TMOs) is critical for tailoring material properties to improve performance and enable new technologies. Despite extensive research efforts, atomic-scale mechanisms underpinning dynamic reactions and reaction-induced phase transitions remain elusive. Here, we use in situ environmental transmission electron microscopy to investigate how water vapor oxidizes vacancy-ordered SrCoO<sub>2.5</sub> at moderately elevated temperatures, demonstrating that water molecules can initiate oxidation more effectively than oxygen under comparable conditions. We discover a distinct "staging" behavior during the oxidation process: A fully ordered intermediate phase, SrCoO<sub>2.75</sub>, forms before transitioning into a near-perovskite SrCoO<sub>3-δ</sub>. In addition, antiphase boundaries, originating at step terraces of SrTiO<sub>3</sub>, alleviate strain by creating reversible nanoscale "gaps" during lattice contraction under oxidation, providing a pathway for preserving structural integrity throughout redox cycling. This work provides atomic-level guidance for engineering TMOs by leveraging water vapor to control their redox behavior and tailor functional properties.