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We report Ca2–xIrO4 nanocrystals exhibit record stability of 300 h continuous operation and high iridium mass activity (248 A gIr–1 at 1.5 VRHE) that is about 62 times that of benchmark IrO2. Lattice-resolution images and surface-sensitive spectroscopies demonstrate the Ir-rich surface layer (evolved from one-dimensional connected edge-sharing IrO6 octahedrons) with high relative content of Ir5+ sites, which is responsible for the high activity and long-term stability. Combining operando infrared spectroscopy with X-ray absorption spectroscopy, we report the first direct observation of key intermediates absorbing at 946 cm–1 (Ir6+═O site) and absorbing at 870 cm–1 (Ir6+OO– site) on iridium-based oxides electrocatalysts, and further discover the Ir6+═O and Ir6+OO– intermediates are stable even just from 1.3 VRHE. Density functional theory calculations indicate the catalytic activity of Ca2IrO4 is enhanced remarkably after surface Ca leaching, and suggest IrOO– and Ir═O intermediates can be stabilized on positive charged active sites of Ir-rich surface layer.
Li et al. (Thu,) studied this question.