A nucleus-coupled electron transfer mechanism for TiO2-catalyzed water splitting
Literature Information
Michael Lucking, Yi-Yang Sun, Damien West, Shengbai Zhang
Based on first-principles calculations, we reveal that in the photocatalytic oxygen evolution reaction (OER) at the TiO2/water interface, the formation of an O–O bond always involves the anti-bonding σ2p* state elevated from the valence band into the conduction band of TiO2 regardless of a detailed reaction pathway. The role of photoholes is to deplete this anti-bonding state once it emerges into the band gap. The reaction barrier is thus determined by the onset where photoholes enter the reaction. This process represents a new reaction mechanism, termed nucleus-coupled electron transfer (NCET), where electron transfer is enabled by the movement of nuclei that promotes the reactive orbital to become the frontier orbital. The NCET mechanism for the OER is shown to exhibit an overall kinetic barrier surmountable at room temperature.
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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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