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Title: Ordered hydroxyls on Ca 3Ru 2O 7(001)

Abstract

As complex ternary perovskite-type oxides are increasingly used in solid oxide fuel cells, electrolysis and catalysis, it is necessary to obtain a better understanding of their surface chemical properties. Here we report a pronounced ordering of hydroxyls on the cleaved (001) surface of the Ruddlesden-Popper perovskite Ca 3Ru 2O 7 upon water adsorption at 105 K and subsequent annealing to room temperature. Density functional theory calculations predict the dissociative adsorption of a single water molecule (E ads = 1.64 eV), forming an (OH) ads group adsorbed in a Ca-Ca bridge site, with an H transferred to a neighboring surface oxygen atom, O surf. Scanning tunneling microscopy images show a pronounced ordering of the hydroxyls with (2 × 1), c(2 × 6), (1 × 3), and (1 × 1) periodicity. The present work demonstrates the importance of octahedral rotation and tilt in perovskites, for influencing surface reactivity, which here induces the ordering of the observed OH overlayers.

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [3];  [3];  [1];  [2];  [2];  [1]
  1. Vienna Univ. of Technology (Austria). Inst. of Applied Physics
  2. Vienna Univ. of Technology (Austria). Inst. of Applied Physics and Center for Computational Materials Science
  3. Tulane Univ., New Orleans, LA (United States). Dept. of Physics and Engineering Physics
Publication Date:
Research Org.:
Tulane Univ., New Orleans, LA (United States)
Sponsoring Org.:
USDOE; National Science Foundation (NSF); Austrian Science Fund (FWF); European Research Council (ERC); Vienna Scientific Cluster (VSC); Louisiana Board of Regents, Baton Rouge, LA (United States)
OSTI Identifier:
1425370
Grant/Contract Number:  
SC0012432
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; Chemical physics; Electrocatalysis; Fuel cells; Surfaces; interfaces and thin films

Citation Formats

Halwidl, Daniel, Mayr-Schmölzer, Wernfried, Fobes, David, Peng, Jin, Mao, Zhiqiang, Schmid, Michael, Mittendorfer, Florian, Redinger, Josef, and Diebold, Ulrike. Ordered hydroxyls on Ca3Ru2O7(001). United States: N. p., 2017. Web. doi:10.1038/s41467-017-00066-w.
Halwidl, Daniel, Mayr-Schmölzer, Wernfried, Fobes, David, Peng, Jin, Mao, Zhiqiang, Schmid, Michael, Mittendorfer, Florian, Redinger, Josef, & Diebold, Ulrike. Ordered hydroxyls on Ca3Ru2O7(001). United States. doi:10.1038/s41467-017-00066-w.
Halwidl, Daniel, Mayr-Schmölzer, Wernfried, Fobes, David, Peng, Jin, Mao, Zhiqiang, Schmid, Michael, Mittendorfer, Florian, Redinger, Josef, and Diebold, Ulrike. Tue . "Ordered hydroxyls on Ca3Ru2O7(001)". United States. doi:10.1038/s41467-017-00066-w. https://www.osti.gov/servlets/purl/1425370.
@article{osti_1425370,
title = {Ordered hydroxyls on Ca3Ru2O7(001)},
author = {Halwidl, Daniel and Mayr-Schmölzer, Wernfried and Fobes, David and Peng, Jin and Mao, Zhiqiang and Schmid, Michael and Mittendorfer, Florian and Redinger, Josef and Diebold, Ulrike},
abstractNote = {As complex ternary perovskite-type oxides are increasingly used in solid oxide fuel cells, electrolysis and catalysis, it is necessary to obtain a better understanding of their surface chemical properties. Here we report a pronounced ordering of hydroxyls on the cleaved (001) surface of the Ruddlesden-Popper perovskite Ca3Ru2O7 upon water adsorption at 105 K and subsequent annealing to room temperature. Density functional theory calculations predict the dissociative adsorption of a single water molecule (Eads = 1.64 eV), forming an (OH)ads group adsorbed in a Ca-Ca bridge site, with an H transferred to a neighboring surface oxygen atom, Osurf. Scanning tunneling microscopy images show a pronounced ordering of the hydroxyls with (2 × 1), c(2 × 6), (1 × 3), and (1 × 1) periodicity. The present work demonstrates the importance of octahedral rotation and tilt in perovskites, for influencing surface reactivity, which here induces the ordering of the observed OH overlayers.},
doi = {10.1038/s41467-017-00066-w},
journal = {Nature Communications},
number = 1,
volume = 8,
place = {United States},
year = {Tue Jun 20 00:00:00 EDT 2017},
month = {Tue Jun 20 00:00:00 EDT 2017}
}

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Works referenced in this record:

The interaction of water with solid surfaces: Fundamental aspects
journal, October 1987


Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

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