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

Colin F. Dickens, Joseph H. Montoya, Ambarish R. Kulkarni, Michal Bajdich, Jens K. Nørskov*

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

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. Finally, 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.
Original languageEnglish
JournalSurface Science
Volume681
Pages (from-to)122-129
Number of pages8
ISSN0039-6028
DOIs
Publication statusPublished - 2019

Keywords

  • Catalysis
  • Electronic structure
  • Oxygen
  • Oxygen evolution reaction
  • Surface

Cite this

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. In: Surface Science. 2019 ; Vol. 681. pp. 122-129.
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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. Finally, 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.",
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year = "2019",
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language = "English",
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An electronic structure descriptor for oxygen reactivity at metal and metal-oxide surfaces. / Dickens, Colin F.; Montoya, Joseph H.; Kulkarni, Ambarish R.; Bajdich, Michal; Nørskov, Jens K.

In: Surface Science, Vol. 681, 2019, p. 122-129.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - An electronic structure descriptor for oxygen reactivity at metal and metal-oxide surfaces

AU - Dickens, Colin F.

AU - Montoya, Joseph H.

AU - Kulkarni, Ambarish R.

AU - Bajdich, Michal

AU - Nørskov, Jens K.

PY - 2019

Y1 - 2019

N2 - 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. Finally, 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.

AB - 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. Finally, 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.

KW - Catalysis

KW - Electronic structure

KW - Oxygen

KW - Oxygen evolution reaction

KW - Surface

U2 - 10.1016/j.susc.2018.11.019

DO - 10.1016/j.susc.2018.11.019

M3 - Journal article

VL - 681

SP - 122

EP - 129

JO - Surface Science

JF - Surface Science

SN - 0039-6028

ER -