Exceptionally Robust Face-Sharing Motifs Enable Efficient and Durable Water Oxidation

Corner-sharing oxides usually suffer from structural reconstruction during the bottleneck oxygen-evolution reaction (OER) in water electrolysis. Therefore, introducing dynamically stable active sites in an alternative structure is urgent but challenging. Here, 1D 5H-polytype Ba₅Bi_0.25Co_3.75FeO_14−δ oxide with face-sharing motifs is identified as a highly active and stable candidate for alkaline OER. Benefiting from the stable face-sharing motifs with three couples of combined bonds, Ba₅Bi_0.25Co_3.75FeO_14−δ can maintain its local structures even under high OER potentials as evidenced by fast operando spectroscopy, contributing to a negligible performance degradation over 110 h. Besides, the higher Co valence and smaller orbital bandgap in Ba₅Bi_0.25Co_3.75FeO_14−δ endow it with a much better electron transport ability than its corner-sharing counterpart, leading to a distinctly reduced overpotential of 308 mV at 10 mA cm⁻² in 0.1 m KOH. Further mechanism studies show that the short distance between lattice-oxygen sites in face-sharing Ba₅Bi_0.25Co_3.75FeO_14−δ can accelerate the deprotonation step (*OOH + OH⁻ = *OO + H₂O + e⁻) via a steric inductive effect to promote lattice-oxygen participation. In this work, not only is a new 1D face-sharing oxide with impressive OER performance discovered, but also a rational design of dynamic stable and active sites for sustainable energy systems is inaugurated.