Formation of O adatom pairs and charge transfer upon O2 dissociation on reduced TiO2(110)

Literature Information

Publication Date 2010-03-25
DOI 10.1039/C000250J
Impact Factor 3.676
Authors

Yingge Du, Nathaniel A. Deskins, Zhenrong Zhang, Zdenek Dohnalek, Michel Dupuis, Igor Lyubinetsky


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Abstract

Scanning tunneling microscopy and density functional theory have been used to investigate the details of O2 dissociation leading to the formation of oxygen adatom (Oa) pairs at terminal Ti sites. An intermediate, metastable Oa–Oa configuration with two nearest-neighbor O atoms is observed after O2 dissociation at 300 K. The nearest-neighbor Oa pairs are destabilized by Coulomb repulsion of charged Oa's and separate further along the Ti row into energetically more favorable second-nearest neighbor configuration. The potential energy profile calculated for O2 dissociation on Ti rows and following Oa's separation strongly supports the experimental observations. Furthermore, our results suggest that the itinerant electrons associated with the O vacancies (VO) are being utilized in the O2 dissociation process at the Ti row. Experimentally this is supported by the observation that not all VO's can be healed by O2 exposure at 300 K, as some VO's becoming less reactive due to supplying certain charge to Oa's. Further, theoretical results show that at least two oxygen vacancies per O2 molecule are required in order for the O2 dissociation at the Ti row to become viable.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

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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