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Two Pathways for Water Interaction with Oxygen Adatoms on TiO2(110) Surfaces

Conference ·
OSTI ID:988665
Atomic-level investigation of the interaction of H2O with a partially re-oxidized TiO2(110) has been performed at 300 K by combining scanning tunneling microscopy and density functional theory. In particular, we demonstrate that oxygen adatoms (Oa), produced during O2 exposure of reduced TiO2(110) surfaces, alter water dissociation/ recombination chemistry through two different pathways. When H2O diffuses to Oa on the same Ti row, it becomes trapped near the Oa, exchanges a proton easily to dissociate and form a pair of terminal hydroxyls (OHt) along the row, which can then readily recombine and re-dissociate many times or overcome the barrier to move away. When H2O passes along the Oa on an adjacent row, an across-row proton transfer facilitated by the bridging O atom results in spontaneous dissociation of H2O on a Ti trough leading to the formation of a stable across-row OHt pair, which after awhile can recombine and H2O diffuses away. The across-row process has not been reported previously, and it starts from a ‘‘pseudo-dissociated’’ state of water. We also show how the H2O dissociation and OHt pair statistical reformation induce an apparent along- or across-row shift of Oa as a result of the oxygen scrambling process between H2O and Oa.
Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Organization:
USDOE
DOE Contract Number:
AC05-76RL01830
OSTI ID:
988665
Report Number(s):
PNNL-SA-67667; 19392; 19804; KP1704020
Country of Publication:
United States
Language:
English

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