Efficient Oxygen Electrocatalysis by Nanostructured Mixed-Metal Oxides
Abstract
Oxygen electrocatalysis plays a critical role in the efficiency of important energy conversion and storage systems. While many efforts have focused on designing efficient electrocatalysts for these processes, optimal catalysts that are inexpensive, active, selective, and stable are still being searched. Nonstoichiometric, mixed-metal oxides present a promising group of electrocatalysts for these processes due to the versatility of the surface composition and fast oxygen conducting properties. Herein, we demonstrate, using a combination of theoretical and experimental studies, the ability to develop design principles that can be used to engineer oxygen electrocatalysis activity of layered, mixed ionic-electronic conducting Ruddlesden– Popper (R–P) oxides. We show that a density function theory (DFT) derived descriptor, O2 binding energy on a surface oxygen vacancy, can be effective in identifying efficient R–P oxide structures for oxygen reduction reaction (ORR). Using a controlled synthesis method, well-defined nanostructures of R–P oxides are obtained, which along with thermochemical and electrochemical activity studies are used to validate the design principles. This has led to the identification of a highly active ORR electrocatalyst, nanostructured Co-doped lanthanum nickelate oxide, which when incorporated in solid oxide fuel cell cathodes significantly enhances the performance at intermediate temperatures (~550 °C), while maintaining long-term stability. Here,more »
- Publication Date:
- Research Org.:
- Wayne State Univ., Detroit, MI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1487017
- Grant/Contract Number:
- SC0014347
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 140; Journal Issue: 26; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Gu, Xiang -Kui, Carneiro, Juliana S. A., Samira, Samji, Das, Anirban, Ariyasingha, Nuwandi M., and Nikolla, Eranda. Efficient Oxygen Electrocatalysis by Nanostructured Mixed-Metal Oxides. United States: N. p., 2018.
Web. doi:10.1021/jacs.7b11138.
Gu, Xiang -Kui, Carneiro, Juliana S. A., Samira, Samji, Das, Anirban, Ariyasingha, Nuwandi M., & Nikolla, Eranda. Efficient Oxygen Electrocatalysis by Nanostructured Mixed-Metal Oxides. United States. https://doi.org/10.1021/jacs.7b11138
Gu, Xiang -Kui, Carneiro, Juliana S. A., Samira, Samji, Das, Anirban, Ariyasingha, Nuwandi M., and Nikolla, Eranda. Wed .
"Efficient Oxygen Electrocatalysis by Nanostructured Mixed-Metal Oxides". United States. https://doi.org/10.1021/jacs.7b11138. https://www.osti.gov/servlets/purl/1487017.
@article{osti_1487017,
title = {Efficient Oxygen Electrocatalysis by Nanostructured Mixed-Metal Oxides},
author = {Gu, Xiang -Kui and Carneiro, Juliana S. A. and Samira, Samji and Das, Anirban and Ariyasingha, Nuwandi M. and Nikolla, Eranda},
abstractNote = {Oxygen electrocatalysis plays a critical role in the efficiency of important energy conversion and storage systems. While many efforts have focused on designing efficient electrocatalysts for these processes, optimal catalysts that are inexpensive, active, selective, and stable are still being searched. Nonstoichiometric, mixed-metal oxides present a promising group of electrocatalysts for these processes due to the versatility of the surface composition and fast oxygen conducting properties. Herein, we demonstrate, using a combination of theoretical and experimental studies, the ability to develop design principles that can be used to engineer oxygen electrocatalysis activity of layered, mixed ionic-electronic conducting Ruddlesden– Popper (R–P) oxides. We show that a density function theory (DFT) derived descriptor, O2 binding energy on a surface oxygen vacancy, can be effective in identifying efficient R–P oxide structures for oxygen reduction reaction (ORR). Using a controlled synthesis method, well-defined nanostructures of R–P oxides are obtained, which along with thermochemical and electrochemical activity studies are used to validate the design principles. This has led to the identification of a highly active ORR electrocatalyst, nanostructured Co-doped lanthanum nickelate oxide, which when incorporated in solid oxide fuel cell cathodes significantly enhances the performance at intermediate temperatures (~550 °C), while maintaining long-term stability. Here, the reported findings demonstrate the effectiveness of the developed design principles to engineer mixed ionic-electronic conducting oxides for efficient oxygen electrocatalysis, and the potential of nanostructured Co-doped lanthanum nickelate oxides as promising catalysts for oxygen electrocatalysis.},
doi = {10.1021/jacs.7b11138},
journal = {Journal of the American Chemical Society},
number = 26,
volume = 140,
place = {United States},
year = {Wed May 30 00:00:00 EDT 2018},
month = {Wed May 30 00:00:00 EDT 2018}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 37 works
Citation information provided by
Web of Science
Web of Science
Figures / Tables:
Figure S1: The structures of B-site terminated (001) surfaces for first-series R-P oxides with mixed B-site transition metals. The cyan, green/blue, and red spheres represent La, transition metal, and O atoms, respectively.
All figures and tables
(26 total)
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Alloys of platinum and early transition metals as oxygen reduction electrocatalysts
journal, September 2009
- Greeley, J.; Stephens, I. E. L.; Bondarenko, A. S.
- Nature Chemistry, Vol. 1, Issue 7, p. 552-556
Effect of pretreatment atmosphere on the particle size and oxygen reduction activity of low-loading platinum impregnated titanium carbide powder electrocatalysts
journal, August 2015
- Yang, Leerang; Kimmel, Yannick C.; Lu, Qi
- Journal of Power Sources, Vol. 287
High-performance Ag–Co alloy catalysts for electrochemical oxygen reduction
journal, August 2014
- Holewinski, Adam; Idrobo, Juan-Carlos; Linic, Suljo
- Nature Chemistry, Vol. 6, Issue 9
Density functional theory-based electrochemical models for the oxygen reduction reaction: Comparison of modeling approaches for electric field and solvent effects
journal, September 2011
- Yeh, Kuan-Yu; Janik, Michael J.
- Journal of Computational Chemistry, Vol. 32, Issue 16
Stabilization of ultrathin (hydroxy)oxide films on transition metal substrates for electrochemical energy conversion
journal, May 2017
- Zeng, Zhenhua; Chang, Kee-Chul; Kubal, Joseph
- Nature Energy, Vol. 2, Issue 6
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
Atomic Ensemble and Electronic Effects in Ag-Rich AgPd Nanoalloy Catalysts for Oxygen Reduction in Alkaline Media
journal, May 2012
- Slanac, Daniel A.; Hardin, William G.; Johnston, Keith P.
- Journal of the American Chemical Society, Vol. 134, Issue 23
Competitive Oxygen Evolution in Acid Electrolyte Catalyzed at Technologically Relevant Electrodes Painted with Nanoscale RuO 2
journal, January 2017
- DeSario, Paul A.; Chervin, Christopher N.; Nelson, Eric S.
- ACS Applied Materials & Interfaces, Vol. 9, Issue 3
Lowering the Temperature of Solid Oxide Fuel Cells
journal, November 2011
- Wachsman, E. D.; Lee, K. T.
- Science, Vol. 334, Issue 6058
A high-performance cathode for the next generation of solid-oxide fuel cells
journal, September 2004
- Shao, Zongping; Haile, Sossina M.
- Nature, Vol. 431, Issue 7005, p. 170-173
Switching on electrocatalytic activity in solid oxide cells
journal, August 2016
- Myung, Jae-ha; Neagu, Dragos; Miller, David N.
- Nature, Vol. 537, Issue 7621
High Temperature Electrolysis in Alkaline Cells, Solid Proton Conducting Cells, and Solid Oxide Cells
journal, October 2014
- Ebbesen, Sune Dalgaard; Jensen, Søren Højgaard; Hauch, Anne
- Chemical Reviews, Vol. 114, Issue 21
Factors Governing Oxygen Reduction in Solid Oxide Fuel Cell Cathodes †
journal, October 2004
- Adler, Stuart B.
- Chemical Reviews, Vol. 104, Issue 10
Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface
journal, June 2016
- Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin
- Nature Materials, Vol. 15, Issue 9
Real-time impedance monitoring of oxygen reduction during surface modification of thin film cathodes
journal, March 2017
- Rupp, Ghislain M.; Opitz, Alexander K.; Nenning, Andreas
- Nature Materials, Vol. 16, Issue 6
Impedance of Solid Oxide Fuel Cell LSM/YSZ Composite Cathodes
journal, January 2001
- Jørgensen, M. J.; Mogensen, M.
- Journal of The Electrochemical Society, Vol. 148, Issue 5
Engineering Complex, Layered Metal Oxides: High-Performance Nickelate Oxide Nanostructures for Oxygen Exchange and Reduction
journal, June 2015
- Ma, Xianfeng; Carneiro, Juliana S. A.; Gu, Xiang-Kui
- ACS Catalysis, Vol. 5, Issue 7
A Low-Operating-Temperature Solid Oxide Fuel Cell in Hydrocarbon-Air Mixtures
journal, June 2000
- Hibino, T.
- Science, Vol. 288, Issue 5473
Advances in layered oxide cathodes for intermediate temperature solid oxide fuel cells
journal, January 2010
- Tarancón, Albert; Burriel, Mónica; Santiso, José
- Journal of Materials Chemistry, Vol. 20, Issue 19
Materials for Intermediate-Temperature Solid-Oxide Fuel Cells
journal, July 2014
- Kilner, John A.; Burriel, Mónica
- Annual Review of Materials Research, Vol. 44, Issue 1
A kinetic study of oxygen reduction reaction on La2NiO4 cathodes by means of impedance spectroscopy
journal, December 2007
- Escudero, M. J.; Aguadero, A.; Alonso, J. A.
- Journal of Electroanalytical Chemistry, Vol. 611, Issue 1-2
La2NiO4+δ as cathode for SOFC: Reactivity study with YSZ and CGO electrolytes
journal, June 2010
- Hernández, A. Montenegro; Mogni, L.; Caneiro, A.
- International Journal of Hydrogen Energy, Vol. 35, Issue 11
Oxygen Reduction Reaction Kinetics in Sr-Doped La 2 NiO 4+δ Ruddlesden-Popper Phase as Cathode for Solid Oxide Fuel Cells
journal, January 2015
- Guan, Bo; Li, Wenyuan; Zhang, Hui
- Journal of The Electrochemical Society, Vol. 162, Issue 7
La2NiO4+δ infiltrated into gadolinium doped ceria as novel solid oxide fuel cell cathodes: Electrochemical performance and impedance modelling
journal, October 2015
- Nicollet, C.; Flura, A.; Vibhu, V.
- Journal of Power Sources, Vol. 294
Novel La 2 NiO 4+δ and La 4 Ni 3 O 10−δ composites for solid oxide fuel cell cathodes
journal, December 2013
- Woolley, Russell J.; Skinner, Stephen J.
- Journal of Power Sources, Vol. 243
Kinetics of Oxygen Surface Exchange on Epitaxial Ruddlesden–Popper Phases and Correlations to First-Principles Descriptors
journal, January 2016
- Lee, Yueh-Lin; Lee, Dongkyu; Wang, Xiao Renshaw
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 2
Characterisation of La2NiO4+δ using in-situ high temperature neutron powder diffraction
journal, March 2003
- Skinner, Stephen J.
- Solid State Sciences, Vol. 5, Issue 3
Oxygen Tracer Diffusion in La2-xSrxCuO4-y Single Crystals
journal, September 1993
- Opila, Elizabeth J.; Tuller, Harry L.; Wuensch, Bernhardt J.
- Journal of the American Ceramic Society, Vol. 76, Issue 9
Mechanism and kinetics of oxygen reduction on porous La1−Sr CoO3− electrodes
journal, August 1998
- Adler, S. B.
- Solid State Ionics, Vol. 111, Issue 1-2
Electro- and thermal-catalysis by layered, first series Ruddlesden-Popper oxides
journal, November 2016
- Das, Anirban; Xhafa, Enxhi; Nikolla, Eranda
- Catalysis Today, Vol. 277
Segregated Chemistry and Structure on (001) and (100) Surfaces of (La 1– x Sr x ) 2 CoO 4 Override the Crystal Anisotropy in Oxygen Exchange Kinetics
journal, July 2015
- Chen, Yan; Téllez, Helena; Burriel, Mónica
- Chemistry of Materials, Vol. 27, Issue 15
Design of Ruddlesden–Popper Oxides with Optimal Surface Oxygen Exchange Properties for Oxygen Reduction and Evolution
journal, August 2017
- Gu, Xiang-Kui; Nikolla, Eranda
- ACS Catalysis, Vol. 7, Issue 9
Properties of La2−xPrxNiO4 cathode for intermediate-temperature solid oxide fuel cells
journal, January 2011
- Nishimoto, Shunsuke; Takahashi, Suguru; Kameshima, Yoshikazu
- Journal of the Ceramic Society of Japan, Vol. 119, Issue 1387
Oxygen diffusion and transport properties in non-stoichiometric LnNiO oxides
journal, November 2005
- Boehm, E.; Bassat, J.; Dordor, P.
- Solid State Ionics, Vol. 176, Issue 37-38
Strontium influence on the oxygen electrocatalysis of La 2−x Sr x NiO 4±δ (0.0 ≤ x Sr ≤ 1.0) thin films
journal, January 2014
- Lee, Dongkyu; Lee, Yueh-Lin; Grimaud, Alexis
- J. Mater. Chem. A, Vol. 2, Issue 18
Optimizing cathode materials for intermediate-temperature solid oxide fuel cells (SOFCs): Oxygen reduction on nanostructured lanthanum nickelate oxides
journal, January 2017
- Carneiro, Juliana Silva Alves; Brocca, Roger Antunes; Lucena, Max Laylson Ribeiro Sampaio
- Applied Catalysis B: Environmental, Vol. 200
Absence of Ni on the outer surface of Sr doped La 2 NiO 4 single crystals
journal, January 2014
- Burriel, Mónica; Wilkins, Stuart; Hill, John P.
- Energy Environ. Sci., Vol. 7, Issue 1
Surface termination and subsurface restructuring of perovskite-based solid oxide electrode materials
journal, January 2014
- Druce, J.; Téllez, H.; Burriel, M.
- Energy Environ. Sci., Vol. 7, Issue 11
Oxygen transport properties of La2Ni1−xCuxO4+δ mixed conducting oxides
journal, July 2003
- Boehm, E.; Bassat, J. -M.; Steil, M. C.
- Solid State Sciences, Vol. 5, Issue 7
Mass transport in La2Ni1−xCoxO4+δ oxides with the K2NiF4 structure
journal, December 2002
- Kilner, J.
- Solid State Ionics, Vol. 154-155
Oxygen transport in the LaNiCoO system
journal, July 2005
- Munnings, C.; Skinner, S.; Amow, G.
- Solid State Ionics, Vol. 176, Issue 23-24
Oxygen Sponges for Electrocatalysis: Oxygen Reduction/Evolution on Nonstoichiometric, Mixed Metal Oxides
journal, April 2018
- Gu, Xiang-Kui; Samira, Samji; Nikolla, Eranda
- Chemistry of Materials, Vol. 30, Issue 9
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Oxygen Electrocatalysis on Epitaxial La 0.6 Sr 0.4 CoO 3- δ Perovskite Thin Films for Solid Oxide Fuel Cells
journal, January 2012
- Crumlin, Ethan J.; Ahn, Sung-Jin; Lee, Dongkyu
- Journal of The Electrochemical Society, Vol. 159, Issue 7
Synthesis, Structure, and Properties of Ln4Ni3O10-δ (Ln = La, Pr, and Nd)
journal, July 1995
- Zhang, Z.; Greenblatt, M.
- Journal of Solid State Chemistry, Vol. 117, Issue 2
Neutron diffraction, synchrotron radiation and EXAFS spectroscopy study of crystal structure peculiarities of the lanthanum nickelates Lan+1NinOy (n=1,2,3)
journal, September 2001
- Voronin, V. I.; Berger, I. F.; Cherepanov, V. A.
- Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 470, Issue 1-2
Oxidation energies of transition metal oxides within the framework
journal, May 2006
- Wang, Lei; Maxisch, Thomas; Ceder, Gerbrand
- Physical Review B, Vol. 73, Issue 19
Determination of oxygen adsorption–desorption rates and diffusion rate coefficients in perovskites at different oxygen partial pressures by a microkinetic approach
journal, January 2015
- Rochoux, M.; Guo, Y.; Schuurman, Y.
- Physical Chemistry Chemical Physics, Vol. 17, Issue 2
Recent Approaches in Mechanistic and Kinetic Studies of Catalytic Reactions Using SSITKA Technique
journal, November 2014
- Ledesma, Cristian; Yang, Jia; Chen, De
- ACS Catalysis, Vol. 4, Issue 12
Anisotropic oxygen diffusion in tetragonal La 2 NiO 4+δ : molecular dynamics calculations
journal, January 2010
- Chroneos, Alexander; Parfitt, David; Kilner, John A.
- J. Mater. Chem., Vol. 20, Issue 2
Atomistic computer simulation of oxygen ion conduction mechanisms in La2NiO4
journal, September 2008
- Cleave, A. R.; Kilner, J. A.; Skinner, S. J.
- Solid State Ionics, Vol. 179, Issue 21-26
Interstitialcy diffusion of oxygen in tetragonal La 2 CoO 4 + δ
journal, January 2011
- Kushima, Akihiro; Parfitt, David; Chroneos, Alexander
- Phys. Chem. Chem. Phys., Vol. 13, Issue 6
Effect of A and B-site cations on surface exchange coefficient for ABO3 perovskite materials
journal, January 2013
- Armstrong, Eric N.; Duncan, Keith L.; Wachsman, Eric D.
- Physical Chemistry Chemical Physics, Vol. 15, Issue 7
Low energy ion scattering (LEIS). A practical introduction to its theory, instrumentation, and applications
journal, January 2016
- Cushman, Cody V.; Brüner, Philipp; Zakel, Julia
- Anal. Methods, Vol. 8, Issue 17
Reducibility of Co at the La 0.8 Sr 0.2 CoO 3 /(La 0.5 Sr 0.5 ) 2 CoO 4 hetero-interface at elevated temperatures
journal, January 2014
- Tsvetkov, Nikolai; Chen, Yan; Yildiz, Bilge
- Journal of Materials Chemistry A, Vol. 2, Issue 35
Preparation and characterization of LaMn1$minus;xCUxO3+$lambda; perovskite oxides
journal, July 1990
- Rojas, M.
- Journal of Catalysis, Vol. 124, Issue 1
XPS study of copper aluminate catalysts
journal, May 1980
- Ertl, G.; Hierl, R.; Knözinger, H.
- Applications of Surface Science, Vol. 5, Issue 1
Fermi Level shifting, Charge Transfer and Induced Magnetic Coupling at La0.7Ca0.3MnO3/LaNiO3 Interface
journal, February 2015
- Ning, Xingkun; Wang, Zhanjie; Zhang, Zhidong
- Scientific Reports, Vol. 5, Issue 1
Determination of peak positions and areas from wide-scan XPS spectra
journal, March 1990
- Turner, N. H.; Single, A. M.
- Surface and Interface Analysis, Vol. 15, Issue 3
X-ray photoelectron studies on some oxides and hydroxides of cobalt, nickel, and copper
journal, November 1975
- McIntyre, N. S.; Cook, M. G.
- Analytical Chemistry, Vol. 47, Issue 13
Carbon nanotube growth on Ni-particles prepared in situ by reduction of La2NiO4
journal, May 2001
- Liang, Q.; Gao, L. Z.; Li, Q.
- Carbon, Vol. 39, Issue 6
Reaction Kinetics of Gas–Solid Exchange Using Gas Phase Isotopic Oxygen Exchange
journal, August 2016
- Huang, Yi-Lin; Pellegrinelli, Christopher; Wachsman, Eric D.
- ACS Catalysis, Vol. 6, Issue 9
Recent developments in Ruddlesden–Popper nickelate systems for solid oxide fuel cell cathodes
journal, April 2006
- Amow, G.; Skinner, S. J.
- Journal of Solid State Electrochemistry, Vol. 10, Issue 8
Ba0.5Sr0.5Co0.8Fe0.2O3−δ as a cathode for IT-SOFCs with a GDC interlayer
journal, September 2006
- Duan, Zaoshu; Yang, Min; Yan, Aiyu
- Journal of Power Sources, Vol. 160, Issue 1
Effect of unsintered gadolinium-doped ceria buffer layer on performance of metal-supported solid oxide fuel cells using unsintered barium strontium cobalt ferrite cathode
journal, October 2010
- Kim, Yu-Mi; Kim-Lohsoontorn, Pattaraporn; Bae, Joongmyeon
- Journal of Power Sources, Vol. 195, Issue 19
Works referencing / citing this record:
Nanoengineering of solid oxide electrochemical cell technologies: An outlook
journal, March 2019
- Carneiro, Juliana; Nikolla, Eranda
- Nano Research, Vol. 12, Issue 9
N-Doped ordered porous carbon decorated with WN and Ni nanoparticles for enhanced electrocatalytic properties
journal, January 2020
- Ma, Yiou; Guo, Hu; Xue, Hairong
- Journal of Porous Materials, Vol. 27, Issue 3
Engineering the Interface of Carbon Electrocatalysts at the Triple Point for Enhanced Oxygen Reduction Reaction
journal, June 2018
- Qiao, Mo; Titirici, Maria‐Magdalena
- Chemistry – A European Journal, Vol. 24, Issue 69
Trends in Oxygen Electrocatalysis of 3 d ‐Layered (Oxy)(Hydro)Oxides
journal, June 2019
- Zhao, Zhenghang; Schlexer Lamoureux, Philomena; Kulkarni, Ambarish
- ChemCatChem, Vol. 11, Issue 15
Azadirachta indica leaf-extract-assisted synthesis of CoO–NiO mixed metal oxide for application in a microbial fuel cell as a cathode catalyst
journal, January 2019
- Noori, Md. T.; Tiwari, B. R.; Ghangrekar, M. M.
- Sustainable Energy & Fuels, Vol. 3, Issue 12
Figures / Tables found in this record:
Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.