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

Title: Tuning the Electronic Structure of LaNiO 3 through Alloying with Strontium to Enhance Oxygen Evolution Activity

Abstract

The perovskite oxide LaNiO3 is a promising oxygen electrocatalyst for renewable energy storage and conversion technologies. Here, it is shown that strontium substitution for lanthanum in coherently strained, epitaxial LaNiO3 films (La1-xSrxNiO3) significantly enhances the oxygen evolution reaction (OER) activity, resulting in performance at x = 0.5 comparable to the state-of-the-art catalyst Ba0.5Sr0.5Co0.8Fe0.2O3-delta. By combining X-ray photoemission and X-ray absorption spectroscopies with density functional theory, it is shown that an upward energy shift of the O 2p band relative to the Fermi level occurs with increasing x in La1-xSrxNiO3. This alloying step strengthens Ni 3d-O 2p hybridization and decreases the charge transfer energy, which in turn accounts for the enhanced OER activity.

Authors:
 [1];  [2]; ORCiD logo [3];  [4];  [5];  [6];  [7];  [8];  [8];  [9];  [7];  [3];  [3]
  1. State Key Laboratory of Functional Materials for InformaticsShanghai Institute of Microsystem and Information TechnologyChinese Academy of Sciences Shanghai 200050 China, Center for Excellence in Superconducting ElectronicsChinese Academy of Sciences Shanghai 200050 China, Physical and Computational Sciences DirectoratePacific Northwest National Laboratory Richland WA 99354 USA
  2. Physical and Computational Sciences DirectoratePacific Northwest National Laboratory Richland WA 99354 USA, The Key Laboratory of Solar Thermal Energy and Photovoltaic SystemInstitute of Electrical EngineeringChinese Academy of Sciences Beijing 100190 China, Department of PhysicsUniversity of Chinese Academy of Sciences Beijing 100190 China
  3. Physical and Computational Sciences DirectoratePacific Northwest National Laboratory Richland WA 99354 USA
  4. Physical and Computational Sciences DirectoratePacific Northwest National Laboratory Richland WA 99354 USA, School of ChemicalBiological and Environmental EngineeringOregon State University Corvallis OR 97331 USA
  5. X‐Ray Science DivisionAdvanced Photon SourceArgonne National Laboratory Lemont IL 60439 USA
  6. Department of PhysicsFaculty of ScienceNational University of Singapore Singapore 117542 Singapore, NUS Graduate School for Integrative Sciences and EngineeringNational University of Singapore Singapore 117456 Singapore
  7. Department of PhysicsFaculty of ScienceNational University of Singapore Singapore 117542 Singapore
  8. Theoretical Materials PhysicsQ‐MATCesamUniversity of Liège B‐4000 Liège Belgium
  9. Environmental Molecular Sciences LaboratoryPacific Northwest National Laboratory Richland WA 99354 USA
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1568921
Alternate Identifier(s):
OSTI ID: 1568923; OSTI ID: 1571524; OSTI ID: 1574233
Report Number(s):
PNNL-SA-141734
Journal ID: ISSN 2198-3844
Grant/Contract Number:  
AC05-76RL01830; AC02-06CH11357
Resource Type:
Published Article
Journal Name:
Advanced Science
Additional Journal Information:
Journal Name: Advanced Science Journal Volume: 6 Journal Issue: 19; Journal ID: ISSN 2198-3844
Publisher:
Wiley
Country of Publication:
Germany
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; nickelates; LaNiO3; oxygen evolution reaction; hole doping; hybridization

Citation Formats

Liu, Jishan, Jia, Endong, Wang, Le, Stoerzinger, Kelsey A., Zhou, Hua, Tang, Chi Sin, Yin, Xinmao, He, Xu, Bousquet, Eric, Bowden, Mark E., Wee, Andrew T. S., Chambers, Scott A., and Du, Yingge. Tuning the Electronic Structure of LaNiO 3 through Alloying with Strontium to Enhance Oxygen Evolution Activity. Germany: N. p., 2019. Web. doi:10.1002/advs.201901073.
Liu, Jishan, Jia, Endong, Wang, Le, Stoerzinger, Kelsey A., Zhou, Hua, Tang, Chi Sin, Yin, Xinmao, He, Xu, Bousquet, Eric, Bowden, Mark E., Wee, Andrew T. S., Chambers, Scott A., & Du, Yingge. Tuning the Electronic Structure of LaNiO 3 through Alloying with Strontium to Enhance Oxygen Evolution Activity. Germany. doi:10.1002/advs.201901073.
Liu, Jishan, Jia, Endong, Wang, Le, Stoerzinger, Kelsey A., Zhou, Hua, Tang, Chi Sin, Yin, Xinmao, He, Xu, Bousquet, Eric, Bowden, Mark E., Wee, Andrew T. S., Chambers, Scott A., and Du, Yingge. Wed . "Tuning the Electronic Structure of LaNiO 3 through Alloying with Strontium to Enhance Oxygen Evolution Activity". Germany. doi:10.1002/advs.201901073.
@article{osti_1568921,
title = {Tuning the Electronic Structure of LaNiO 3 through Alloying with Strontium to Enhance Oxygen Evolution Activity},
author = {Liu, Jishan and Jia, Endong and Wang, Le and Stoerzinger, Kelsey A. and Zhou, Hua and Tang, Chi Sin and Yin, Xinmao and He, Xu and Bousquet, Eric and Bowden, Mark E. and Wee, Andrew T. S. and Chambers, Scott A. and Du, Yingge},
abstractNote = {The perovskite oxide LaNiO3 is a promising oxygen electrocatalyst for renewable energy storage and conversion technologies. Here, it is shown that strontium substitution for lanthanum in coherently strained, epitaxial LaNiO3 films (La1-xSrxNiO3) significantly enhances the oxygen evolution reaction (OER) activity, resulting in performance at x = 0.5 comparable to the state-of-the-art catalyst Ba0.5Sr0.5Co0.8Fe0.2O3-delta. By combining X-ray photoemission and X-ray absorption spectroscopies with density functional theory, it is shown that an upward energy shift of the O 2p band relative to the Fermi level occurs with increasing x in La1-xSrxNiO3. This alloying step strengthens Ni 3d-O 2p hybridization and decreases the charge transfer energy, which in turn accounts for the enhanced OER activity.},
doi = {10.1002/advs.201901073},
journal = {Advanced Science},
number = 19,
volume = 6,
place = {Germany},
year = {2019},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1002/advs.201901073

Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Spin-State Regulation of Perovskite Cobaltite to Realize Enhanced Oxygen Evolution Activity
journal, November 2017


Interface Structure, Band Alignment, and Built-In Potentials at LaFeO 3 / n SrTiO 3 Heterojunctions
journal, November 2016


Covalency-reinforced oxygen evolution reaction catalyst
journal, September 2015

  • Yagi, Shunsuke; Yamada, Ikuya; Tsukasaki, Hirofumi
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9249

Formation of Two-Dimensional Homologous Faults and Oxygen Electrocatalytic Activities in a Perovskite Nickelate
journal, April 2017


Speciation and Electronic Structure of La1−xSrxCoO3−δ During Oxygen Electrolysis
journal, October 2018

  • Stoerzinger, Kelsey A.; Renshaw Wang, Xiao; Hwang, Jonathan
  • Topics in Catalysis, Vol. 61, Issue 20
  • DOI: 10.1007/s11244-018-1070-7

Band alignment and electrocatalytic activity at the p - n La 0.88 Sr 0.12 FeO 3 /SrTiO 3 (001) heterojunction
journal, June 2018

  • Wang, L.; Du, Y.; Chang, L.
  • Applied Physics Letters, Vol. 112, Issue 26
  • DOI: 10.1063/1.5030897

Phase diagram of compressively strained nickelate thin films
journal, September 2013

  • Disa, A. S.; Kumah, D. P.; Ngai, J. H.
  • APL Materials, Vol. 1, Issue 3
  • DOI: 10.1063/1.4820431

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

Estimating Hybridization of Transition Metal and Oxygen States in Perovskites from O K -edge X-ray Absorption Spectroscopy
journal, January 2014

  • Suntivich, Jin; Hong, Wesley T.; Lee, Yueh-Lin
  • The Journal of Physical Chemistry C, Vol. 118, Issue 4
  • DOI: 10.1021/jp410644j

Tuning Bifunctional Oxygen Electrocatalysts by Changing the A-Site Rare-Earth Element in Perovskite Nickelates
journal, August 2018

  • Wang, Le; Stoerzinger, Kelsey A.; Chang, Lei
  • Advanced Functional Materials, Vol. 28, Issue 39
  • DOI: 10.1002/adfm.201803712

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976


Perovskites in catalysis and electrocatalysis
journal, November 2017


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

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

Heterointerface engineered electronic and magnetic phases of NdNiO3 thin films
journal, November 2013

  • Liu, Jian; Kargarian, Mehdi; Kareev, Mikhail
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3714

Investigation of the metal–insulator transition in NdNiO 3 films by site-selective X-ray absorption spectroscopy
journal, January 2017

  • Palina, Natalia; Wang, Le; Dash, Sibashisa
  • Nanoscale, Vol. 9, Issue 18
  • DOI: 10.1039/C7NR00742F

Quantifying octahedral rotations in strained perovskite oxide films
journal, July 2010


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

Systematic Study of Oxygen Evolution Activity and Stability on La 1– x Sr x FeO 3−δ Perovskite Electrocatalysts in Alkaline Media
journal, March 2018

  • She, Sixuan; Yu, Jie; Tang, Wanqi
  • ACS Applied Materials & Interfaces, Vol. 10, Issue 14
  • DOI: 10.1021/acsami.8b00682

Impact of Strontium-Substitution on Oxygen Evolution Reaction of Lanthanum Nickelates in Alkaline Solution
journal, January 2018

  • Sankannavar, Ravi; Sandeep, K. C.; Kamath, Sachin
  • Journal of The Electrochemical Society, Vol. 165, Issue 15
  • DOI: 10.1149/2.0301815jes

High-Energy Surface X-ray Diffraction for Fast Surface Structure Determination
journal, January 2014


Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO 3 Perovskites
journal, February 2016

  • Petrie, Jonathan R.; Cooper, Valentino R.; Freeland, John W.
  • Journal of the American Chemical Society, Vol. 138, Issue 8
  • DOI: 10.1021/jacs.5b11713

Electronic structure and metal-insulator transition in LaNiO 3 δ
journal, March 2002


Cations in Octahedral Sites: A Descriptor for Oxygen Electrocatalysis on Transition-Metal Spinels
journal, April 2017

  • Wei, Chao; Feng, Zhenxing; Scherer, Günther G.
  • Advanced Materials, Vol. 29, Issue 23
  • DOI: 10.1002/adma.201606800

Character of Holes in Li x Ni 1 x O and Their Magnetic Behavior
journal, January 1989


Water electrolysis on La1−xSrxCoO3−δ perovskite electrocatalysts
journal, March 2016

  • Mefford, J. Tyler; Rong, Xi; Abakumov, Artem M.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11053

Strain Effect on Oxygen Evolution Reaction Activity of Epitaxial NdNiO 3 Thin Films
journal, March 2019

  • Wang, Le; Stoerzinger, Kelsey A.; Chang, Lei
  • ACS Applied Materials & Interfaces, Vol. 11, Issue 13
  • DOI: 10.1021/acsami.8b21301

Covalency-driven unusual metal-insulator transition in nickelates
journal, March 1994


Structural Changes of Cobalt-Based Perovskites upon Water Oxidation Investigated by EXAFS
journal, April 2013

  • Risch, Marcel; Grimaud, Alexis; May, Kevin J.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 17
  • DOI: 10.1021/jp3126768

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

Hybridization-controlled charge transfer and induced magnetism at correlated oxide interfaces
journal, January 2016

  • Grisolia, M. N.; Varignon, J.; Sanchez-Santolino, G.
  • Nature Physics, Vol. 12, Issue 5
  • DOI: 10.1038/nphys3627

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


Epitaxial strain modulated electronic properties of interface controlled nickelate superlattices
journal, July 2018


Asymmetric Orbital-Lattice Interactions in Ultrathin Correlated Oxide Films
journal, September 2011


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


Electronic structure and the metal-insulator transition in LnNiO 3 (Ln=La, Pr, Nd, Sm and Ho): bandstructure results
journal, November 1994


Influence of Strain on the Surface–Oxygen Interaction and the Oxygen Evolution Reaction of SrIrO 3
journal, February 2018

  • Kuo, Ding-Yuan; Eom, C. John; Kawasaki, Jason K.
  • The Journal of Physical Chemistry C, Vol. 122, Issue 8
  • DOI: 10.1021/acs.jpcc.7b12081