DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Competing strain effects in reactivity of LaCoO3 with oxygen

Abstract

Planar strain effects on oxygen-vacancy formation and oxygen adsorption on LaCoO 3 are shown to manifest through competing mechanisms. Through first-principles calculations, we postulate that these unit processes are facilitated by elastic stretching. However, spin-state transitions and Co-O bond exchange hinder these processes by trapping the lattice oxygen with increasing tensile strain. A transition from chemisorption to physisorption of the oxygen molecule is identified at high strains. Insights on charge-density profiles, density of electronic states, and stress thresholds suggest the possibility of tuning strain-mediated reactivity in LaCoO 3 and related perovskite oxides.

Authors:
 [1];  [1];  [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Publication Date:
Research Org.:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1505715
Grant/Contract Number:  
SC0002633
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review. B, Condensed Matter and Materials Physics
Additional Journal Information:
Journal Volume: 82; Journal Issue: 11; Journal ID: ISSN 1098-0121
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Kushima, Akihiro, Yip, Sidney, and Yildiz, Bilge. Competing strain effects in reactivity of LaCoO3 with oxygen. United States: N. p., 2010. Web. doi:10.1103/physrevb.82.115435.
Kushima, Akihiro, Yip, Sidney, & Yildiz, Bilge. Competing strain effects in reactivity of LaCoO3 with oxygen. United States. https://doi.org/10.1103/physrevb.82.115435
Kushima, Akihiro, Yip, Sidney, and Yildiz, Bilge. Fri . "Competing strain effects in reactivity of LaCoO3 with oxygen". United States. https://doi.org/10.1103/physrevb.82.115435. https://www.osti.gov/servlets/purl/1505715.
@article{osti_1505715,
title = {Competing strain effects in reactivity of LaCoO3 with oxygen},
author = {Kushima, Akihiro and Yip, Sidney and Yildiz, Bilge},
abstractNote = {Planar strain effects on oxygen-vacancy formation and oxygen adsorption on LaCoO3 are shown to manifest through competing mechanisms. Through first-principles calculations, we postulate that these unit processes are facilitated by elastic stretching. However, spin-state transitions and Co-O bond exchange hinder these processes by trapping the lattice oxygen with increasing tensile strain. A transition from chemisorption to physisorption of the oxygen molecule is identified at high strains. Insights on charge-density profiles, density of electronic states, and stress thresholds suggest the possibility of tuning strain-mediated reactivity in LaCoO3 and related perovskite oxides.},
doi = {10.1103/physrevb.82.115435},
journal = {Physical Review. B, Condensed Matter and Materials Physics},
number = 11,
volume = 82,
place = {United States},
year = {2010},
month = {9}
}

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

Citation Metrics:
Cited by: 92 works
Citation information provided by
Web of Science

Figures / Tables:

FIG. 1 FIG. 1: (Color online) Simulation models of the LaCoO3 (a) bulk, and (b) surface calculations. Large gray, light blue, and small red large dark, light, and small dark in print spheres indicate La, Co, and O atoms, respectively. Solid lines in the figure indicate the simulation cell.

Save / Share:

Works referenced in this record:

Oxygen ion diffusivity in strained yttria stabilized zirconia: where is the fastest strain?
journal, January 2010

  • Kushima, Akihiro; Yildiz, Bilge
  • Journal of Materials Chemistry, Vol. 20, Issue 23
  • DOI: 10.1039/c000259c

Projector augmented-wave method
journal, December 1994


Structural Parameters of LaCoO 3 near the Spin State Transition
journal, November 2001

  • Xu, Sheng; Moritomo, Yutaka; Mori, Kazuhiro
  • Journal of the Physical Society of Japan, Vol. 70, Issue 11
  • DOI: 10.1143/JPSJ.70.3296

Strain-Induced Insulator State and Giant Gauge Factor of La 0.7 Sr 0.3 CoO 3 Films
journal, February 2008


Atomic-Scale Evidence for an Enhanced Catalytic Reactivity of Stretched Surfaces
journal, June 2003

  • Wintterlin, Joost; Zambelli, Tomaso; Trost, J.
  • Angewandte Chemie International Edition, Vol. 42, Issue 25
  • DOI: 10.1002/anie.200250845

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

Mesoscopic fast ion conduction in nanometre-scale planar heterostructures
journal, December 2000

  • Sata, N.; Eberman, K.; Eberl, K.
  • Nature, Vol. 408, Issue 6815
  • DOI: 10.1038/35050047

Interplay between External Strain and Oxygen Vacancies on a Rutile TiO 2 ( 110 ) Surface
journal, September 2008


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


A model system for strain effects: epitaxial magnetic films on a piezoelectric substrate
journal, September 2009


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


Localized to Itinerant Electronic Transitions in Transition-Metal Oxides with the Perovskite Structure
journal, October 1998

  • Goodenough, J. B.; Zhou, J. -S.
  • Chemistry of Materials, Vol. 10, Issue 10
  • DOI: 10.1021/cm980276u

Strain-induced formation of arrays of catalytically active sites at the metal–oxide interface
journal, April 2004


Optimization of ionic conductivity in doped ceria
journal, February 2006

  • Andersson, D. A.; Simak, S. I.; Skorodumova, N. V.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 10
  • DOI: 10.1073/pnas.0509537103

Factors Governing Oxygen Reduction in Solid Oxide Fuel Cell Cathodes
journal, October 2004


Band theory and Mott insulators: Hubbard U instead of Stoner I
journal, July 1991

  • Anisimov, Vladimir I.; Zaanen, Jan; Andersen, Ole K.
  • Physical Review B, Vol. 44, Issue 3, p. 943-954
  • DOI: 10.1103/PhysRevB.44.943

Pressure-Induced Magnetic Transition in Manganite ( La 0.75 Ca 0.25 MnO 3 )
journal, June 2009


Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation
journal, September 1992


Colossal Ionic Conductivity at Interfaces of Epitaxial ZrO2:Y2O3/SrTiO3 Heterostructures
journal, August 2008

  • Garcia-Barriocanal, J.; Rivera-Calzada, A.; Varela, M.
  • Science, Vol. 321, Issue 5889
  • DOI: 10.1126/science.1156393

First-principles calculations of the electronic structure and spectra of strongly correlated systems: the LDA + U method
journal, January 1997

  • Anisimov, Vladimir I.; Aryasetiawan, F.; Lichtenstein, A. I.
  • Journal of Physics: Condensed Matter, Vol. 9, Issue 4, p. 767-808
  • DOI: 10.1088/0953-8984/9/4/002

Tuning the magnetic properties of La Co O 3 thin films by epitaxial strain
journal, January 2008


Materials for Solid Oxide Fuel Cells
journal, February 2010


Adsorption of atomic and molecular oxygen on the LaMnO3(001) surface: ab initio supercell calculations and thermodynamics
journal, January 2008

  • Kotomin, Eugene A.; Mastrikov, Yuri A.; Heifets, Eugene
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 31
  • DOI: 10.1039/b804378g

Impact of stress on oxygen vacancy ordering in epitaxial (La0.5Sr0.5)CoO3−∂ thin films
journal, May 2003

  • Klenov, Dmitri O.; Donner, Wolfgang; Foran, Brendan
  • Applied Physics Letters, Vol. 82, Issue 20
  • DOI: 10.1063/1.1575503

Origin of Colossal Ionic Conductivity in Oxide Multilayers: Interface Induced Sublattice Disorder
journal, March 2010


Ab initiomolecular dynamics for liquid metals
journal, January 1993


Defect chemistry and surface properties of LaCoO3
journal, January 2000

  • Read, Mark S. D.; Saiful Islam, M.; Watson, Graeme W.
  • Journal of Materials Chemistry, Vol. 10, Issue 10
  • DOI: 10.1039/b002168g

Oxidation energies of transition metal oxides within the GGA + U framework
journal, May 2006


Ab initio energetics of La B O 3 ( 001 ) ( B = Mn , Fe, Co, and Ni) for solid oxide fuel cell cathodes
journal, December 2009


Structural effects on the spin-state transition in epitaxially strained LaCoO 3 films
journal, February 2009


First-principles study for low-spin LaCoO 3 with a structurally consistent Hubbard U
journal, March 2009


Structural phenomena associated with the spin-state transition in LaCoO 3
journal, September 2002


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


Atomic Oxygen Adsorption on Au(111) Surfaces with Defects
journal, January 2009

  • Baker, Thomas A.; Friend, Cynthia M.; Kaxiras, Efthimios
  • The Journal of Physical Chemistry C, Vol. 113, Issue 8
  • DOI: 10.1021/jp806952z

Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets
journal, May 2021


Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect
journal, February 2020


Works referencing / citing this record:

Strain Control of Oxygen Vacancies in Epitaxial Strontium Cobaltite Films
journal, January 2016

  • Petrie, Jonathan R.; Mitra, Chandrima; Jeen, Hyoungjeen
  • Advanced Functional Materials, Vol. 26, Issue 10
  • DOI: 10.1002/adfm.201504868

Enhancing Electrocatalytic Water Splitting by Strain Engineering
journal, February 2019


Interfacial Lattice‐Strain‐Driven Generation of Oxygen Vacancies in an Aerobic‐Annealed TiO 2 (B) Electrode
journal, November 2019


Nanostructured Materials and Interfaces for Advanced Ionic Electronic Conducting Oxides
journal, May 2019

  • Acosta, Matias; Baiutti, Federico; Tarancón, Albert
  • Advanced Materials Interfaces, Vol. 6, Issue 15
  • DOI: 10.1002/admi.201900462

Chemomechanics of ionically conductive ceramics for electrical energy conversion and storage
journal, January 2014


Atomic Layer Deposition for Surface Engineering of Solid Oxide Fuel Cell Electrodes
journal, March 2019

  • Shim, Joon Hyung; Han, Gwon Deok; Choi, Hyung Jong
  • International Journal of Precision Engineering and Manufacturing-Green Technology, Vol. 6, Issue 3
  • DOI: 10.1007/s40684-019-00092-7

Equilibrium oxygen storage capacity of ultrathin CeO2-δ depends non-monotonically on large biaxial strain
journal, May 2017

  • Balaji Gopal, Chirranjeevi; García-Melchor, Max; Lee, Sang Chul
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms15360

Valence-state reflectometry of complex oxide heterointerfaces
journal, September 2016


Activating cobalt(II) oxide nanorods for efficient electrocatalysis by strain engineering
journal, November 2017


Oxygen diffusion in solid oxide fuel cell cathode and electrolyte materials: mechanistic insights from atomistic simulations
journal, January 2011

  • Chroneos, Alexander; Yildiz, Bilge; Tarancón, Albert
  • Energy & Environmental Science, Vol. 4, Issue 8
  • DOI: 10.1039/c0ee00717j

Mechanism for enhanced oxygen reduction kinetics at the (La,Sr)CoO3−δ/(La,Sr)2CoO4+δ hetero-interface
journal, January 2012

  • Han, Jeong Woo; Yildiz, Bilge
  • Energy & Environmental Science, Vol. 5, Issue 9
  • DOI: 10.1039/c2ee03592h

Strain effects on oxygen migration in perovskites
journal, January 2015

  • Mayeshiba, Tam; Morgan, Dane
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 4
  • DOI: 10.1039/c4cp05554c

Quantifying the origin of inter-adsorbate interactions on reactive surfaces for catalyst screening and design
journal, January 2015

  • Krishnamoorthy, Aravind; Yildiz, Bilge
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 34
  • DOI: 10.1039/c5cp03143e

Amorphous-cathode-route towards low temperature SOFC
journal, January 2018

  • Cavallaro, Andrea; Pramana, Stevin S.; Ruiz-Trejo, Enrique
  • Sustainable Energy & Fuels, Vol. 2, Issue 4
  • DOI: 10.1039/c7se00606c

Charge transfer-induced O p-band center shift for an enhanced OER performance in LaCoO 3 film
journal, January 2019

  • Liu, Zhongyuan; Sun, Yu; Wu, Xiaofeng
  • CrystEngComm, Vol. 21, Issue 10
  • DOI: 10.1039/c8ce01849a

An in operando study of chemical expansion and oxygen surface exchange rates in epitaxial GdBaCo 2 O 5.5 electrodes in a solid-state electrochemical cell by time-resolved X-ray diffraction
journal, January 2018

  • Chatterjee, Arindom; Caicedo, Jose Manuel; Ballesteros, Belén
  • Journal of Materials Chemistry A, Vol. 6, Issue 26
  • DOI: 10.1039/c8ta02790k

Strain-controlled oxygen vacancy formation and ordering in CaMnO 3
journal, August 2013


Strain-driven oxygen deficiency in multiferroic SrMnO 3 thin films
journal, September 2016


Structural, electronic, and magnetic properties of bulk and epitaxial LaCoO 3 through diffusion Monte Carlo
journal, December 2019


“Stretching” the energy landscape of oxides—Effects on electrocatalysis and diffusion
journal, February 2014


Controlling the Oxygen Electrocatalysis on Perovskite and Layered Oxide Thin Films for Solid Oxide Fuel Cell Cathodes
journal, March 2019

  • Yang, Gene; Jung, Wonsang; Ahn, Sung-Jin
  • Applied Sciences, Vol. 9, Issue 5
  • DOI: 10.3390/app9051030

Nanostructured Materials and Interfaces for Advanced Ionic Electronic Conducting Oxides
text, January 2019

  • Acosta, Matias; Baiutti, F.; Tarancón, A.
  • Apollo - University of Cambridge Repository
  • DOI: 10.17863/cam.54560

Strain-controlled oxygen vacancy formation and ordering in CaMnO₃
text, January 2013

  • Spaldin, Nicola A.; Grande, Tor; Selbach, Sverre M.
  • American Physical Society
  • DOI: 10.7892/boris.72980

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.