Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 17, Issue 26, Pages 16779-16783Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c5cp01202c
Keywords
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Funding
- NSF [DMR-1104994]
- DOE [DE-SC0002623]
- NERSC under DOE [DE-AC02-05CH11231]
- CCNI at RPI
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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 sigma(2p)* 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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