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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. 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.

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
Alternate Identifier(s):
OSTI ID: 1636053
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. https://doi.org/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. https://doi.org/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}
}

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Cited by: 21 works
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Works referenced in this record:

Why gold is the noblest of all the metals
journal, July 1995


Electronic factors determining the reactivity of metal surfaces
journal, December 1995


Alloy catalysts designed from first principles
journal, October 2004

  • Greeley, Jeff; Mavrikakis, Manos
  • Nature Materials, Vol. 3, Issue 11
  • DOI: 10.1038/nmat1223

Modification of the surface electronic and chemical properties of Pt(111) by subsurface 3d transition metals
journal, June 2004

  • Kitchin, J. R.; Nørskov, J. K.; Barteau, M. A.
  • The Journal of Chemical Physics, Vol. 120, Issue 21
  • DOI: 10.1063/1.1737365

Effect of Strain on the Reactivity of Metal Surfaces
journal, September 1998


Trends in CO Oxidation Rates for Metal Nanoparticles and Close-Packed, Stepped, and Kinked Surfaces
journal, May 2009

  • Jiang, T.; Mowbray, D. J.; Dobrin, S.
  • The Journal of Physical Chemistry C, Vol. 113, Issue 24
  • DOI: 10.1021/jp811185g

Scaling Properties of Adsorption Energies for Hydrogen-Containing Molecules on Transition-Metal Surfaces
journal, July 2007


Towards the computational design of solid catalysts
journal, April 2009

  • Nørskov, J.; Bligaard, T.; Rossmeisl, J.
  • Nature Chemistry, Vol. 1, Issue 1, p. 37-46
  • DOI: 10.1038/nchem.121

The Brønsted–Evans–Polanyi relation and the volcano curve in heterogeneous catalysis
journal, May 2004


Fast Prediction of Adsorption Properties for Platinum Nanocatalysts with Generalized Coordination Numbers
journal, June 2014

  • Calle-Vallejo, Federico; Martínez, José I.; García-Lastra, Juan M.
  • Angewandte Chemie International Edition, Vol. 53, Issue 32
  • DOI: 10.1002/anie.201402958

Introducing structural sensitivity into adsorption–energy scaling relations by means of coordination numbers
journal, April 2015

  • Calle-Vallejo, Federico; Loffreda, David; Koper, Marc T. M.
  • Nature Chemistry, Vol. 7, Issue 5
  • DOI: 10.1038/nchem.2226

Finding optimal surface sites on heterogeneous catalysts by counting nearest neighbors
journal, October 2015


Structure-Sensitive Scaling Relations: Adsorption Energies from Surface Site Stability
journal, March 2018


Orbitalwise Coordination Number for Predicting Adsorption Properties of Metal Nanocatalysts
journal, January 2017


Overcoming Site Heterogeneity In Search of Metal Nanocatalysts
journal, September 2018


General Structure–Reactivity Relationship for Oxygen on Transition-Metal Oxides
journal, May 2017

  • Fung, Victor; Tao, Franklin Feng; Jiang, De-en
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 10
  • DOI: 10.1021/acs.jpclett.7b00861

A universal principle for a rational design of single-atom electrocatalysts
journal, April 2018


Bond-Energy-Integrated Descriptor for Oxygen Electrocatalysis of Transition Metal Oxides
journal, June 2018


A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles
journal, October 2011


Number of outer electrons as descriptor for adsorption processes on transition metals and their oxides
journal, January 2013

  • Calle-Vallejo, Federico; Inoglu, Nilay G.; Su, Hai-Yan
  • Chemical Science, Vol. 4, Issue 3
  • DOI: 10.1039/c2sc21601a

Effects of strain, d -band filling, and oxidation state on the surface electronic structure and reactivity of 3 d perovskite surfaces
journal, August 2012

  • Akhade, Sneha A.; Kitchin, John R.
  • The Journal of Chemical Physics, Vol. 137, Issue 8
  • DOI: 10.1063/1.4746117

Electronic Origin of the Surface Reactivity of Transition-Metal-Doped TiO 2 (110)
journal, December 2012

  • García-Mota, Mónica; Vojvodic, Aleksandra; Abild-Pedersen, Frank
  • The Journal of Physical Chemistry C, Vol. 117, Issue 1
  • DOI: 10.1021/jp310667r

Relating the electronic structure and reactivity of the 3d transition metal monoxide surfaces
journal, July 2014


Relationships between the surface electronic and chemical properties of doped 4d and 5d late transition metal dioxides
journal, March 2015

  • Xu, Zhongnan; Kitchin, John R.
  • The Journal of Chemical Physics, Vol. 142, Issue 10
  • DOI: 10.1063/1.4914093

Optimizing Perovskites for the Water-Splitting Reaction
journal, December 2011


Trends in adsorption of electrocatalytic water splitting intermediates on cubic ABO 3 oxides
journal, January 2018

  • Montoya, Joseph H.; Doyle, Andrew D.; Nørskov, Jens K.
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 5
  • DOI: 10.1039/C7CP06539F

Prediction of solid oxide fuel cell cathode activity with first-principles descriptors
journal, January 2011

  • Lee, Yueh-Lin; Kleis, Jesper; Rossmeisl, Jan
  • Energy & Environmental Science, Vol. 4, Issue 10
  • DOI: 10.1039/c1ee02032c

Double perovskites as a family of highly active catalysts for oxygen evolution in alkaline solution
journal, September 2013

  • Grimaud, Alexis; May, Kevin J.; Carlton, Christopher E.
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3439

Charge-transfer-energy-dependent oxygen evolution reaction mechanisms for perovskite oxides
journal, January 2017

  • Hong, Wesley T.; Stoerzinger, Kelsey A.; Lee, Yueh-Lin
  • Energy & Environmental Science, Vol. 10, Issue 10
  • DOI: 10.1039/C7EE02052J

Electronic Structure of Chemically-Delithiated LiCoO 2 Studied by Electron Energy-Loss Spectrometry
journal, February 2002

  • Graetz, J.; Hightower, A.; Ahn, C. C.
  • The Journal of Physical Chemistry B, Vol. 106, Issue 6
  • DOI: 10.1021/jp0133283

Nonrigid Band Behavior of the Electronic Structure of LiCoO 2 Thin Film during Electrochemical Li Deintercalation
journal, June 2014

  • Ensling, D.; Cherkashinin, G.; Schmid, S.
  • Chemistry of Materials, Vol. 26, Issue 13
  • DOI: 10.1021/cm501480b

Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces
journal, March 2011

  • Man, Isabela C.; Su, Hai‐Yan; Calle‐Vallejo, Federico
  • ChemCatChem, Vol. 3, Issue 7
  • DOI: 10.1002/cctc.201000397

Understanding trends in C–H bond activation in heterogeneous catalysis
journal, October 2016

  • Latimer, Allegra A.; Kulkarni, Ambarish R.; Aljama, Hassan
  • Nature Materials, Vol. 16, Issue 2
  • DOI: 10.1038/nmat4760

Combining theory and experiment in electrocatalysis: Insights into materials design
journal, January 2017


QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

An object-oriented scripting interface to a legacy electronic structure code
journal, January 2002

  • Bahn, S. R.; Jacobsen, K. W.
  • Computing in Science & Engineering, Vol. 4, Issue 3
  • DOI: 10.1109/5992.998641

Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals
journal, March 1999


Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation
journal, June 2012


Electrolysis of water on (oxidized) metal surfaces
journal, December 2005


Electrolysis of water on oxide surfaces
journal, September 2007


A Theoretical Investigation into the Role of Surface Defects for Oxygen Evolution on RuO 2
journal, August 2017

  • Dickens, Colin F.; Nørskov, Jens K.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 34
  • DOI: 10.1021/acs.jpcc.7b03481

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011


Matplotlib: A 2D Graphics Environment
journal, January 2007


Works referencing / citing this record:

Quadruple perovskite ruthenate as a highly efficient catalyst for acidic water oxidation
journal, August 2019


The role of metastability in enhancing water-oxidation activity
journal, January 2019

  • Vonrüti, Nathalie; Aschauer, Ulrich
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 44
  • DOI: 10.1039/c9cp04859f

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

Theory-guided design of catalytic materials using scaling relationships and reactivity descriptors
journal, November 2019


Progress and Challenges Toward the Rational Design of Oxygen Electrocatalysts Based on a Descriptor Approach
journal, November 2019


Fast prediction of oxygen reduction reaction activity on carbon nanotubes with a localized geometric descriptor
journal, January 2020

  • Yang, Kunran; Zaffran, Jeremie; Yang, Bo
  • Physical Chemistry Chemical Physics, Vol. 22, Issue 2
  • DOI: 10.1039/c9cp04885e

Defects‐Induced In‐Plane Heterophase in Cobalt Oxide Nanosheets for Oxygen Evolution Reaction
journal, October 2019


Key role of antibonding electron transfer in bonding on solid surfaces
journal, September 2019


Probing the impact of surface reactivity on charge transport in dimensional phase changed tungsten films
journal, March 2019

  • Chattaraj, Ananya; Khan, Saif; Walczak, Lukasz
  • Journal of Materials Science: Materials in Electronics, Vol. 30, Issue 9
  • DOI: 10.1007/s10854-019-01145-y

The role of metastability in enhancing water-oxidation activity
text, January 2019