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Title: Generalizable, Electroless, Template-Assisted Synthesis and Electrocatalytic Mechanistic Understanding of Perovskite LaNiO3 Nanorods as Viable, Supportless Oxygen Evolution Reaction Catalysts in Alkaline Media

Abstract

We present that the oxygen evolution reaction (OER) is a key reaction for water electrolysis cells and air-powered battery applications. However, conventional metal oxide catalysts, used for high-performing OER, tend to incorporate comparatively expensive and less abundant precious metals such as Ru and Ir, and, moreover, suffer from poor stability. To attempt to mitigate for all of these issues, we have prepared one-dimensional (1D) OER-active perovskite nanorods using a unique, simple, generalizable, and robust method. Significantly, our work demonstrates the feasibility of a novel electroless, seedless, surfactant-free, wet solution-based protocol for fabricating “high aspect ratio” LaNiO3 and LaMnO3 nanostructures. As the main focus of our demonstration of principle, we prepared as-synthesized LaNiO3 rods and correlated the various temperatures at which these materials were annealed with their resulting OER performance. In addition, we observed generally better OER performance for samples prepared with lower annealing temperatures. Specifically, when annealed at 600 °C, in the absence of a conventional conductive carbon support, our as-synthesized LaNiO3 rods not only evinced (i) a reasonable level of activity toward OER but also displayed (ii) an improved stability, as demonstrated by chronoamperometric measurements, especially when compared with a control sample of commercially available (and more expensive) RuO2.

Authors:
 [1];  [1];  [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [2]
  1. Department of Chemistry, State University of New York at Stony Brook, Stony Brook, New York 11794-3400, United States
  2. Department of Chemistry, State University of New York at Stony Brook, Stony Brook, New York 11794-3400, United States, Condensed Matter Physics and Materials Sciences Division, Brookhaven National Laboratory, Building 480, Upton, New York 11973, United States
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1371491
Alternate Identifier(s):
OSTI ID: 1376134
Report Number(s):
BNL-114070-2017-JA
Journal ID: ISSN 1944-8244
Grant/Contract Number:  
SC0012704
Resource Type:
Published Article
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Name: ACS Applied Materials and Interfaces; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; catalysis; electrochemistry; oxygen evolution reaction; perovskite; template synthesis

Citation Formats

McBean, Coray L., Liu, Haiqing, Scofield, Megan E., Li, Luyao, Wang, Lei, Bernstein, Ashley, and Wong, Stanislaus S. Generalizable, Electroless, Template-Assisted Synthesis and Electrocatalytic Mechanistic Understanding of Perovskite LaNiO3 Nanorods as Viable, Supportless Oxygen Evolution Reaction Catalysts in Alkaline Media. United States: N. p., 2017. Web. doi:10.1021/acsami.7b06855.
McBean, Coray L., Liu, Haiqing, Scofield, Megan E., Li, Luyao, Wang, Lei, Bernstein, Ashley, & Wong, Stanislaus S. Generalizable, Electroless, Template-Assisted Synthesis and Electrocatalytic Mechanistic Understanding of Perovskite LaNiO3 Nanorods as Viable, Supportless Oxygen Evolution Reaction Catalysts in Alkaline Media. United States. https://doi.org/10.1021/acsami.7b06855
McBean, Coray L., Liu, Haiqing, Scofield, Megan E., Li, Luyao, Wang, Lei, Bernstein, Ashley, and Wong, Stanislaus S. Mon . "Generalizable, Electroless, Template-Assisted Synthesis and Electrocatalytic Mechanistic Understanding of Perovskite LaNiO3 Nanorods as Viable, Supportless Oxygen Evolution Reaction Catalysts in Alkaline Media". United States. https://doi.org/10.1021/acsami.7b06855.
@article{osti_1371491,
title = {Generalizable, Electroless, Template-Assisted Synthesis and Electrocatalytic Mechanistic Understanding of Perovskite LaNiO3 Nanorods as Viable, Supportless Oxygen Evolution Reaction Catalysts in Alkaline Media},
author = {McBean, Coray L. and Liu, Haiqing and Scofield, Megan E. and Li, Luyao and Wang, Lei and Bernstein, Ashley and Wong, Stanislaus S.},
abstractNote = {We present that the oxygen evolution reaction (OER) is a key reaction for water electrolysis cells and air-powered battery applications. However, conventional metal oxide catalysts, used for high-performing OER, tend to incorporate comparatively expensive and less abundant precious metals such as Ru and Ir, and, moreover, suffer from poor stability. To attempt to mitigate for all of these issues, we have prepared one-dimensional (1D) OER-active perovskite nanorods using a unique, simple, generalizable, and robust method. Significantly, our work demonstrates the feasibility of a novel electroless, seedless, surfactant-free, wet solution-based protocol for fabricating “high aspect ratio” LaNiO3 and LaMnO3 nanostructures. As the main focus of our demonstration of principle, we prepared as-synthesized LaNiO3 rods and correlated the various temperatures at which these materials were annealed with their resulting OER performance. In addition, we observed generally better OER performance for samples prepared with lower annealing temperatures. Specifically, when annealed at 600 °C, in the absence of a conventional conductive carbon support, our as-synthesized LaNiO3 rods not only evinced (i) a reasonable level of activity toward OER but also displayed (ii) an improved stability, as demonstrated by chronoamperometric measurements, especially when compared with a control sample of commercially available (and more expensive) RuO2.},
doi = {10.1021/acsami.7b06855},
journal = {ACS Applied Materials and Interfaces},
number = ,
volume = ,
place = {United States},
year = {Mon Jul 17 00:00:00 EDT 2017},
month = {Mon Jul 17 00:00:00 EDT 2017}
}

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https://doi.org/10.1021/acsami.7b06855

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Works referenced in this record:

Co3O4 nanocrystals on single-walled carbon nanotubes as a highly efficient oxygen-evolving catalyst
journal, July 2012


Silver decorated LaMnO3 nanorod/graphene composite electrocatalysts as reversible metal-air battery electrodes
journal, April 2017


Synthesis of nanocrystalline conducting composite oxides based on a non-ion selective combined complexing process for functional applications
journal, December 2006


Thermodynamic explanation of the universal correlation between oxygen evolution activity and corrosion of oxide catalysts
journal, July 2015

  • Binninger, Tobias; Mohamed, Rhiyaad; Waltar, Kay
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep12167

On Activity and Stability of Rhombohedral LaNiO3 Catalyst towards ORR and OER in Alkaline Electrolyte
journal, January 2015

  • Sakthivel, M.; Bhandari, S.; Drillet, J. -F.
  • ECS Electrochemistry Letters, Vol. 4, Issue 6
  • DOI: 10.1149/2.0081506eel

Highly Active, Nonprecious Metal Perovskite Electrocatalysts for Bifunctional Metal–Air Battery Electrodes
journal, March 2013

  • Hardin, William G.; Slanac, Daniel A.; Wang, Xiqing
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 8
  • DOI: 10.1021/jz400595z

Highly Enhanced Electrocatalytic Oxygen Reduction Performance Observed in Bimetallic Palladium-Based Nanowires Prepared under Ambient, Surfactantless Conditions
journal, January 2012

  • Koenigsmann, Christopher; Sutter, Eli; Chiesa, Thomas A.
  • Nano Letters, Vol. 12, Issue 4, p. 2013-2020
  • DOI: 10.1021/nl300033e

Optical conductivity of LaNiO 3 : Coherent transport and correlation driven mass enhancement
journal, October 2010


Oxygen deficiency, vacancy clustering and ionic transport in (La,Sr)CoO3−δ
journal, June 2011


Oxygen vacancy induced metal-insulator transition in LaNiO3
journal, January 2016


Porous Perovskite LaNiO3 Nanocubes as Cathode Catalysts for Li-O2 Batteries with Low Charge Potential
journal, August 2014

  • Zhang, Jian; Zhao, Yubao; Zhao, Xiao
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep06005

Evidence of oxygen-vacancy-induced ferromagnetic order in single crystal Mn-doped SrTiO 3
journal, July 2012

  • Middey, Srimanta; Meneghini, Carlo; Ray, Sugata
  • Applied Physics Letters, Vol. 101, Issue 4
  • DOI: 10.1063/1.4738785

Rational design of the electrode morphology for oxygen evolution – enhancing the performance for catalytic water oxidation
journal, January 2014

  • Zeradjanin, Aleksandar R.; Topalov, Angel A.; Van Overmeere, Quentin
  • RSC Advances, Vol. 4, Issue 19
  • DOI: 10.1039/c3ra45998e

Investigation of a “Two‐State” Tafel Phenomenon for the Oxygen Evolution Reaction on an Amorphous Ni‐Co Alloy
journal, November 1995

  • Lian, K. K.; Kirk, D. W.; Thorpe, S. J.
  • Journal of The Electrochemical Society, Vol. 142, Issue 11
  • DOI: 10.1149/1.2048402

Epitaxial growth and surface metallic nature of LaNiO3 thin films
journal, June 2008

  • Tsubouchi, K.; Ohkubo, I.; Kumigashira, H.
  • Applied Physics Letters, Vol. 92, Issue 26
  • DOI: 10.1063/1.2955534

Design Insights for Tuning the Electrocatalytic Activity of Perovskite Oxides for the Oxygen Evolution Reaction
journal, April 2015

  • Malkhandi, S.; Trinh, P.; Manohar, Aswin K.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 15
  • DOI: 10.1021/jp512722x

Enhanced Susceptibility in L NiO 3 Perovskites ( L = L a , P r , N d , N d 0.5 Sm 0.5 )
journal, January 2000


Electro-optics of perovskite solar cells
journal, December 2014

  • Lin, Qianqian; Armin, Ardalan; Nagiri, Ravi Chandra Raju
  • Nature Photonics, Vol. 9, Issue 2
  • DOI: 10.1038/nphoton.2014.284

One-dimensional nanostructures: fabrication, characterisation and applications
journal, July 2008

  • Weber, Jessica; Singhal, Rahul; Zekri, Souhail
  • International Materials Reviews, Vol. 53, Issue 4
  • DOI: 10.1179/174328008X348183

A New Family of Perovskite Catalysts for Oxygen-Evolution Reaction in Alkaline Media: BaNiO 3 and BaNi 0.83 O 2.5
journal, March 2016

  • Lee, Jin Goo; Hwang, Jeemin; Hwang, Ho Jung
  • Journal of the American Chemical Society, Vol. 138, Issue 10
  • DOI: 10.1021/jacs.6b00036

Physicochemical and electrocatalytic properties of LaNiO3 prepared by a low-temperature route for anode application in alkaline water electrolysis
journal, December 1995

  • Singh, R. N.; Jain, A. N.; Tiwari, S. K.
  • Journal of Applied Electrochemistry, Vol. 25, Issue 12
  • DOI: 10.1007/BF00242541

Hollandite Structure K x ≈0.25 IrO 2 Catalyst with Highly Efficient Oxygen Evolution Reaction
journal, December 2015

  • Sun, Wei; Song, Ya; Gong, Xue-Qing
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 1
  • DOI: 10.1021/acsami.5b10159

Vacancy defects and monopole dynamics in oxygen-deficient pyrochlores
journal, April 2014

  • Sala, G.; Gutmann, M. J.; Prabhakaran, D.
  • Nature Materials, Vol. 13, Issue 5
  • DOI: 10.1038/nmat3924

Microstructures of lanthanum nickel oxide particles with crystal facets synthesized in molten chlorides
journal, January 2015

  • Ueno, Shintaro; Sakamoto, Yasunao; Taguchi, Hiroya
  • Journal of the Ceramic Society of Japan, Vol. 123, Issue 1437
  • DOI: 10.2109/jcersj2.123.351

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


Electrocatalytic Measurement Methodology of Oxide Catalysts Using a Thin-Film Rotating Disk Electrode
journal, January 2010

  • Suntivich, Jin; Gasteiger, Hubert A.; Yabuuchi, Naoaki
  • Journal of The Electrochemical Society, Vol. 157, Issue 8
  • DOI: 10.1149/1.3456630

Sodium hypochlorite and its use as an endodontic irrigant
journal, August 1998


Effect of conductive LaNiO3 electrode on the structural and ferroelectric properties of Bi3.25La0.75Ti3O12 films
journal, December 2006

  • Jain, M.; Kang, B. S.; Jia, Q. X.
  • Applied Physics Letters, Vol. 89, Issue 24
  • DOI: 10.1063/1.2404949

Transport properties and metal–insulator transition in oxygen deficient LaNiO 3 : a density functional theory study
journal, September 2016


Ultrathin Nanowires-A Materials Chemistry Perspective
journal, March 2009


Ambient Surfactantless Synthesis, Growth Mechanism, and Size-Dependent Electrocatalytic Behavior of High-Quality, Single Crystalline Palladium Nanowires
journal, September 2011

  • Koenigsmann, Christopher; Santulli, Alexander C.; Sutter, Eli
  • ACS Nano, Vol. 5, Issue 9, p. 7471-7487
  • DOI: 10.1021/nn202434r

Growth of nanowires
journal, March 2008

  • Wang, N.; Cai, Y.; Zhang, R. Q.
  • Materials Science and Engineering: R: Reports, Vol. 60, Issue 1-6, p. 1-51
  • DOI: 10.1016/j.mser.2008.01.001

Synthesis, characterization and electrochemical performance of battery grade NiOOH
journal, August 2005


Strongly coupled thermal and chemical expansion in the perovskite oxide system Sr(Ti,Fe)O 3−α
journal, January 2015

  • Perry, Nicola H.; Kim, Jae Jin; Bishop, Sean R.
  • Journal of Materials Chemistry A, Vol. 3, Issue 7
  • DOI: 10.1039/C4TA05247A

First-principles study of oxygen-deficient LaNiO 3 structures
journal, October 2015


Insulating-layer formation of metallic LaNiO 3 on Nb-doped SrTiO 3 substrate
journal, March 2015

  • Yoo, Hyang Keun; Chang, Young Jun; Moreschini, Luca
  • Applied Physics Letters, Vol. 106, Issue 12
  • DOI: 10.1063/1.4916225

Oxygen Vacancy Enhanced Photocatalytic Activity of Pervoskite SrTiO 3
journal, October 2014

  • Tan, Huaqiao; Zhao, Zhao; Zhu, Wan-bin
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 21
  • DOI: 10.1021/am5051907

Graphene-Co3O4 nanocomposite as electrocatalyst with high performance for oxygen evolution reaction
journal, January 2015

  • Zhao, Yufei; Chen, Shuangqiang; Sun, Bing
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep07629

Electrocatalysts for oxygen evolution in advanced water electrolysis
journal, January 1985


Enhancing Bi-functional Electrocatalytic Activity of Perovskite by Temperature Shock: A Case Study of LaNiO 3−δ
journal, August 2013

  • Zhou, Wei; Sunarso, Jaka
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 17
  • DOI: 10.1021/jz401169n

Structural and dielectric properties of substituted barium titanate ceramics for capacitor applications
journal, December 2015


Pulsed laser deposition of epitaxial LaNiO3 thin films on buffered Si(100)
journal, March 2001


Lanthanide Aluminates as Dielectrics for Non-Volatile Memory Applications: Material Aspects
journal, January 2011

  • Adelmann, C.; Swerts, J.; Richard, O.
  • Journal of The Electrochemical Society, Vol. 158, Issue 8
  • DOI: 10.1149/1.3596557

Effect of Crystallinity of β - and β bc -Nickel Hydroxide Samples on Chemical Cycling
journal, July 2015

  • Thimmasandra Narayan, Ramesh
  • Indian Journal of Materials Science, Vol. 2015
  • DOI: 10.1155/2015/820193

Highly active Co-doped LaMnO 3 perovskite oxide and N-doped carbon nanotube hybrid bi-functional catalyst for rechargeable zinc–air batteries
journal, November 2015


One-Dimensional Nanostructures: Synthesis, Characterization, and Applications
journal, March 2003


Tuning the Electrocatalytic Activity of Perovskites through Active Site Variation and Support Interactions
journal, June 2014

  • Hardin, William G.; Mefford, J. Tyler; Slanac, Daniel A.
  • Chemistry of Materials, Vol. 26, Issue 11
  • DOI: 10.1021/cm403785q

Temperature-Dependent Polarization in Field-Effect Transport and Photovoltaic Measurements of Methylammonium Lead Iodide
journal, August 2015

  • Labram, John G.; Fabini, Douglas H.; Perry, Erin E.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 18
  • DOI: 10.1021/acs.jpclett.5b01669

Integrating NiCo Alloys with Their Oxides as Efficient Bifunctional Cathode Catalysts for Rechargeable Zinc-Air Batteries
journal, June 2015

  • Liu, Xien; Park, Minjoon; Kim, Min Gyu
  • Angewandte Chemie International Edition, Vol. 54, Issue 33
  • DOI: 10.1002/anie.201503612

LaNiO3/NiO hollow nanofibers with mesoporous wall: a significant improvement in NiO electrodes for supercapacitors
journal, October 2014


The thermal transformation from lanthanum hydroxide to lanthanum hydroxide oxide
journal, June 2006


Hollow spherical La0.8Sr0.2MnO3 perovskite oxide with enhanced catalytic activities for the oxygen reduction reaction
journal, December 2014


Phase transition and thermal depolarization of double perovskite modified low sintering temperature PbTiO 3 piezoelectric ceramics
journal, February 2016


Oxygen Evolution Reaction Electrocatalysis on Transition Metal Oxides and (Oxy)hydroxides: Activity Trends and Design Principles
journal, October 2015


Probing oxygen reduction and oxygen evolution reactions on bifunctional non-precious metal catalysts for metal–air batteries
journal, January 2016

  • Thippani, Thirupathi; Mandal, Sudip; Wang, Guanxiong
  • RSC Advances, Vol. 6, Issue 75
  • DOI: 10.1039/C6RA13414A

Toward the rational design of non-precious transition metal oxides for oxygen electrocatalysis
journal, January 2015

  • Hong, Wesley T.; Risch, Marcel; Stoerzinger, Kelsey A.
  • Energy & Environmental Science, Vol. 8, Issue 5
  • DOI: 10.1039/C4EE03869J

Pd-Pt Bimetallic Nanodendrites with High Activity for Oxygen Reduction
journal, May 2009


Structural effects of LaNiO3 as electrocatalyst for the oxygen reduction reaction
journal, April 2017

  • Retuerto, María; Pereira, Amaru González; Pérez-Alonso, Francisco J.
  • Applied Catalysis B: Environmental, Vol. 203
  • DOI: 10.1016/j.apcatb.2016.10.016

In situ formation of oxygen vacancy in perovskite Sr0.95Ti0.8Nb0.1M0.1O3 (M = Mn, Cr) toward efficient carbon dioxide electrolysis
journal, November 2014

  • Zhang, Jun; Xie, Kui; Wei, Haoshan
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep07082

Electronic and crystal structure of fully strained LaNiO 3 films
journal, September 2003


A Fundamental Relationship between Reaction Mechanism and Stability in Metal Oxide Catalysts for Oxygen Evolution
journal, January 2016


Characterization of Electrochemically Prepared γ‐NiOOH by XPS
journal, July 1994

  • Mansour, A. N.; Melendres, C. A.
  • Surface Science Spectra, Vol. 3, Issue 3
  • DOI: 10.1116/1.1247756

Structure and water oxidation activity of 3 d metal oxides: Structure and water oxidation activity
journal, December 2015

  • Li, Ye-Fei; Liu, Zhi-Pan
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 6, Issue 1
  • DOI: 10.1002/wcms.1236