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

Abstract

Activating the O 2 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 Ca 3Ru 2O 7, a Ruddlesden–Popper perovskite, supports a full monolayer of superoxide ions, O 2 -, when exposed to molecular O 2. The electrons for activating the molecule are transferred from the subsurface RuO 2 layer. Theoretical calculations using both, density functional theory (DFT) and more accurate methods (RPA), predict the adsorption of O 2 - 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 O 2 - 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 Omore » 2.« less

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [2];  [2];  [2];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Technische Univ. Wien, Vienna (Austria)
  2. Tulane Univ., New Orleans, LA (United States)
Publication Date:
Research Org.:
Louisiana Board of Regents, Baton Rouge, LA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1425710
Alternate Identifier(s):
OSTI ID: 1499256
Grant/Contract Number:  
SC0012432
Resource Type:
Published Article
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 6; Journal Issue: 14; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Halwidl, Daniel, Mayr-Schmölzer, Wernfried, Setvin, Martin, Fobes, David, Peng, Jin, Mao, Zhiqiang, Schmid, Michael, Mittendorfer, Florian, Redinger, Josef, and Diebold, Ulrike. A full monolayer of superoxide: oxygen activation on the unmodified Ca3Ru2O7(001) surface. United States: N. p., 2018. Web. doi:10.1039/c8ta00265g.
Halwidl, Daniel, Mayr-Schmölzer, Wernfried, Setvin, Martin, Fobes, David, Peng, Jin, Mao, Zhiqiang, Schmid, Michael, Mittendorfer, Florian, Redinger, Josef, & Diebold, Ulrike. A full monolayer of superoxide: oxygen activation on the unmodified Ca3Ru2O7(001) surface. United States. doi:10.1039/c8ta00265g.
Halwidl, Daniel, Mayr-Schmölzer, Wernfried, Setvin, Martin, Fobes, David, Peng, Jin, Mao, Zhiqiang, Schmid, Michael, Mittendorfer, Florian, Redinger, Josef, and Diebold, Ulrike. Mon . "A full monolayer of superoxide: oxygen activation on the unmodified Ca3Ru2O7(001) surface". United States. doi:10.1039/c8ta00265g.
@article{osti_1425710,
title = {A full monolayer of superoxide: oxygen activation on the unmodified Ca3Ru2O7(001) surface},
author = {Halwidl, Daniel and Mayr-Schmölzer, Wernfried and Setvin, Martin and Fobes, David and Peng, Jin and Mao, Zhiqiang and Schmid, Michael and Mittendorfer, Florian and Redinger, Josef and Diebold, Ulrike},
abstractNote = {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 Eads = 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.},
doi = {10.1039/c8ta00265g},
journal = {Journal of Materials Chemistry. A},
number = 14,
volume = 6,
place = {United States},
year = {2018},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/c8ta00265g

Citation Metrics:
Cited by: 3 works
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Works referenced in this record:

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

  • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
  • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
  • DOI: 10.1103/PhysRevB.57.1505