skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: An electronic structure descriptor for oxygen reactivity at metal and metal-oxide surfaces

Abstract

Identifying and understanding relationships between the electronic and atomic structure of surfaces and their catalytic activity is an essential step towards the rational design of heterogeneous catalysts for both thermal and electrochemical applications. Herein, we identify a relationship between the atom-projected density of states of surface oxygen and its ability to make and break bonds with the surrounding metal atoms and hydrogen. This structure-property relationship is shown to hold across different classes of materials (metals, rutile metal-oxides, and perovskite metal-oxides) and for different oxygen binding sites ( i.e. different oxygen coordination numbers). We utilize understanding from the d-band model and the simple two-level quantum coupling problem to shed light on the physical origin of this relationship for transition metal surfaces and we hypothesize similar principles extend to the other materials considered. As a result, we demonstrate the utility of the identified descriptor to serve as a tool for high throughput screening of oxygen active sites for large systems where many unique oxygen sites exist and can be computationally expensive to probe individually. As an example, we predict the reactivity of 36 unique oxygen atoms at a kinked RuO 2 extended surface from a single self-consistent DFT calculation.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3];  [4];  [5]
  1. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Stanford Univ., Stanford, CA (United States); Univ. of California, Davis, CA (United States)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  5. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States); Technical Univ. of Denmark, Kongens Lyngby (Denmark)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1506850
Grant/Contract Number:  
[AC02-76SF00515; SC0008685; AC02-05CH11231; DGE-114747]
Resource Type:
Accepted Manuscript
Journal Name:
Surface Science
Additional Journal Information:
[ Journal Volume: 681; Journal Issue: C]; Journal ID: ISSN 0039-6028
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Electronic structure; Catalysis; Surface; Oxygen; Oxygen evolution reaction

Citation Formats

Dickens, Colin F., Montoya, Joseph H., Kulkarni, Ambarish R., Bajdich, Michal, and Nørskov, Jens K. An electronic structure descriptor for oxygen reactivity at metal and metal-oxide surfaces. United States: N. p., 2018. Web. doi:10.1016/j.susc.2018.11.019.
Dickens, Colin F., Montoya, Joseph H., Kulkarni, Ambarish R., Bajdich, Michal, & Nørskov, Jens K. An electronic structure descriptor for oxygen reactivity at metal and metal-oxide surfaces. United States. doi:10.1016/j.susc.2018.11.019.
Dickens, Colin F., Montoya, Joseph H., Kulkarni, Ambarish R., Bajdich, Michal, and Nørskov, Jens K. Sat . "An electronic structure descriptor for oxygen reactivity at metal and metal-oxide surfaces". United States. doi:10.1016/j.susc.2018.11.019. https://www.osti.gov/servlets/purl/1506850.
@article{osti_1506850,
title = {An electronic structure descriptor for oxygen reactivity at metal and metal-oxide surfaces},
author = {Dickens, Colin F. and Montoya, Joseph H. and Kulkarni, Ambarish R. and Bajdich, Michal and Nørskov, Jens K.},
abstractNote = {Identifying and understanding relationships between the electronic and atomic structure of surfaces and their catalytic activity is an essential step towards the rational design of heterogeneous catalysts for both thermal and electrochemical applications. Herein, we identify a relationship between the atom-projected density of states of surface oxygen and its ability to make and break bonds with the surrounding metal atoms and hydrogen. This structure-property relationship is shown to hold across different classes of materials (metals, rutile metal-oxides, and perovskite metal-oxides) and for different oxygen binding sites (i.e. different oxygen coordination numbers). We utilize understanding from the d-band model and the simple two-level quantum coupling problem to shed light on the physical origin of this relationship for transition metal surfaces and we hypothesize similar principles extend to the other materials considered. As a result, we demonstrate the utility of the identified descriptor to serve as a tool for high throughput screening of oxygen active sites for large systems where many unique oxygen sites exist and can be computationally expensive to probe individually. As an example, we predict the reactivity of 36 unique oxygen atoms at a kinked RuO2 extended surface from a single self-consistent DFT calculation.},
doi = {10.1016/j.susc.2018.11.019},
journal = {Surface Science},
number = [C],
volume = [681],
place = {United States},
year = {2018},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 14 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

Two-dimensional ZnO for the selective photoreduction of CO 2
journal, January 2019

  • Zhao, Yanyan; Liu, Nanshu; Zhou, Si
  • Journal of Materials Chemistry A, Vol. 7, Issue 27
  • DOI: 10.1039/c9ta04477a