Crystallographic Symmetry—Governed Oxygen-Defect Chemistry in Perovskite Oxides for Electrocatalytic Water Splitting

Linai Zhou; Jiamu Feng; Kean Zhu; Lingfeng Gao; Weilin Xu; Hui Wang; Jun Wan

Abstract

Electrocatalytic water splitting is a key technology for sustainable hydrogen production, yet the sluggish kinetics of the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) hinder its efficiency. Perovskite oxides (ABO₃) have emerged as promising catalysts owing to their tunable crystal structures, chemical stability, and abundant active sites. While the crystal phase of perovskite oxides is crucial in determining catalytic activity, charge transport, and reaction energetics, the complex interplay between phase transitions, lattice distortions, oxygen vacancy distribution, and electronic structure remains underexplored. This review systematically examines the structural variations across six primary crystal phases of perovskite oxides, including cubic, hexagonal, tetragonal, orthorhombic, rhombohedral, monoclinic, and their effects on catalytic performance. It explores how lattice symmetry, oxygen vacancy distribution, and electronic properties influence reaction pathways and catalytic efficiency in water splitting. Additionally, the review discusses the role of phase transitions, coordination environment adjustments, and defect engineering in optimizing electrocatalytic behavior. Perovskite oxides are categorized by their A-site and B-site metal ion compositions, providing a comprehensive analysis of how these structural variations influence electrocatalytic mechanisms. The insights gained from this review offer crucial guidance for advancing the design of high-performance perovskite oxide catalysts for sustainable water electrolysis.

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