Legitimate intermediates of oxygen evolution on iridium oxide revealed by in situ electrochemical evanescent wave spectroscopy
Literature Information
Hideshi Ooka, Yuanqing Wang, Akira Yamaguchi, Makoto Hatakeyama, Shinichiro Nakamura, Kazuhito Hashimoto, Ryuhei Nakamura
Understanding how the four-electron oxidation of water to dioxygen proceeds in different materials is critical to the rational design of efficient catalysts towards artificial photosynthetic systems. Here, using in situ electrochemical evanescent wave spectroscopy under oxygen-evolving conditions, we report two intermediates of iridium oxide (IrOx), which is the most active and stable catalyst characterized to date in acidic medium. The observed potential dependence of the two intermediates indicated that they were associated with different surface sites, and intermediate scavenging experiments using H2O2 provided insight into their role during catalysis. Notably, an IrV species with an absorption maximum at 450 nm was found to mediate the initial two-electron oxidation of water. Inhibition of the IrV species by H2O2, combined with computational modeling, indicates that the accumulation and concurrent spin-state change of the IrV species is a prerequisite for efficient water oxidation by IrOx electrodes.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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