A full monolayer of superoxide: oxygen activation on the unmodified Ca 3 Ru 2 O 7 (001) surface

Halwidl, Daniel; Mayr-Schmölzer, Wernfried; Setvin, Martin; Fobes, David; Peng, Jin; Mao, Zhiqiang; Schmid, Michael; Mittendorfer, Florian; Redinger, Josef; Diebold, Ulrike

doi:10.1039/C8TA00265G

Title: A full monolayer of superoxide: oxygen activation on the unmodified Ca ₃ Ru ₂ O ₇ (001) surface

Journal Article · Mon Jan 01 00:00:00 EST 2018 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/C8TA00265G· OSTI ID:1425710

^[1]; Mayr-Schmölzer, Wernfried ^[2]; Setvin, Martin ^[1];

^[3]; Peng, Jin ^[3]; Mao, Zhiqiang ^[3]; Schmid, Michael ^[1];

^[2]; Redinger, Josef ^[2];

^[1]

Institute of Applied Physics, TU Wien, 1040 Vienna, Austria
Institute of Applied Physics, TU Wien, 1040 Vienna, Austria, Center for Computational Materials Science
Department of Physics and Engineering Physics, Tulane University, New Orleans, USA

Activating the O₂ molecule is at the heart of a variety of technological applications, most prominently in energy conversion schemes including solid oxide fuel cells, electrolysis, and catalysis. Perovskite oxides, both traditionally-used and novel formulations, are the prime candidates in established and emerging energy devices. This work shows that the as-cleaved and unmodified CaO-terminated (001) surface of Ca₃Ru₂O₇, a Ruddlesden–Popper perovskite, supports a full monolayer of superoxide ions, O₂^-, when exposed to molecular O₂. The electrons for activating the molecule are transferred from the subsurface RuO₂ layer. Theoretical calculations using both, density functional theory (DFT) and more accurate methods (RPA), predict the adsorption of O₂^- with E_ads = 0.72 eV and provide a thorough analysis of the charge transfer. Non-contact atomic force microscopy (nc-AFM) and scanning tunnelling microscopy (STM) are used to resolve single molecules and confirm the predicted adsorption structures. Local contact potential difference (LCPD) and X-ray photoelectron spectroscopy (XPS) measurements on the full monolayer of O₂^- confirm the negative charge state of the molecules. The present study reports the rare case of an oxide surface without dopants, defects, or low-coordinated sites readily activating molecular O₂.

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Research Organization:: Louisiana Board of Regents, Baton Rouge, LA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0012432

OSTI ID:: 1425710

Alternate ID(s):: OSTI ID: 1499256

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Vol. 6 Journal Issue: 14; ISSN 2050-7488

Publisher:: Royal Society of Chemistry (RSC)Copyright Statement

Country of Publication:: United Kingdom

Language:: English

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Cited by: 16 works

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Title: A full monolayer of superoxide: oxygen activation on the unmodified Ca 3 Ru 2 O 7 (001) surface

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Title: A full monolayer of superoxide: oxygen activation on the unmodified Ca ₃ Ru ₂ O ₇ (001) surface