Dynamic Surface Reconstruction Unifies the Electrocatalytic Oxygen Evolution Performance of Nonstoichiometric Mixed Metal Oxides
Abstract
Compositionally versatile, nonstoichiometric, mixed ionic–electronic conducting metal oxides of the form An+1BnO3n+1 (n = 1 → ∞; A = rare-earth-/alkaline-earth-metal cation; B = transition-metal (TM) cation) remain a highly attractive class of electrocatalysts for catalyzing the energy-intensive oxygen evolution reaction (OER). The current design strategies for describing their OER activities are largely derived assuming a static, unchanged view of their surfaces, despite reports of dynamic structural changes to 3d TM-based perovskites during OER. Herein, through variations in the A- and B-site compositions of An+1BnO3n+1 oxides (n = 1 (A2BO4) or n = ∞ (ABO3); A = La, Sr, Ca; B = Mn, Fe, Co, Ni), we show that, in the absence of electrolyte impurities, surface restructuring is universally the source of high OER activity in these oxides and is dependent on the initial oxide composition. Oxide surface restructuring is induced by irreversible A-site cation dissolution, resulting in in situ formation of a TM oxyhydroxide shell on top of the parent oxide core that serves as the active surface for OER. The rate of surface restructuring is found to depend on (i) composition of A-site cations, with alkaline-earth-metal cations dominating lanthanide cation dissolution, (ii) oxide crystal phase, with n = 1more »
- Authors:
-
[1];
[3];
[2];
[1]
- Department of Chemical Engineering and Materials Science, Wayne State University, Detroit, Michigan 48202, United States
- Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States
- Department of Materials Science and Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States
- Publication Date:
- Research Org.:
- Wayne State Univ., Detroit, MI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)
- OSTI Identifier:
- 1829179
- Alternate Identifier(s):
- OSTI ID: 1830885; OSTI ID: 1837499
- Grant/Contract Number:
- AC02-76SF00515; SC0020953
- Resource Type:
- Published Article
- Journal Name:
- JACS Au
- Additional Journal Information:
- Journal Name: JACS Au Journal Volume: 1 Journal Issue: 12; Journal ID: ISSN 2691-3704
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- surface restructuring; oxygen evolution reaction; perovskites; Ruddlesden−Popper oxides; alkaline electrolyzers; cationic dissolution; structure−performance correlations; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Samira, Samji, Hong, Jiyun, Camayang, John Carl A., Sun, Kai, Hoffman, Adam S., Bare, Simon R., and Nikolla, Eranda. Dynamic Surface Reconstruction Unifies the Electrocatalytic Oxygen Evolution Performance of Nonstoichiometric Mixed Metal Oxides. United States: N. p., 2021.
Web. doi:10.1021/jacsau.1c00359.
Samira, Samji, Hong, Jiyun, Camayang, John Carl A., Sun, Kai, Hoffman, Adam S., Bare, Simon R., & Nikolla, Eranda. Dynamic Surface Reconstruction Unifies the Electrocatalytic Oxygen Evolution Performance of Nonstoichiometric Mixed Metal Oxides. United States. https://doi.org/10.1021/jacsau.1c00359
Samira, Samji, Hong, Jiyun, Camayang, John Carl A., Sun, Kai, Hoffman, Adam S., Bare, Simon R., and Nikolla, Eranda. Fri .
"Dynamic Surface Reconstruction Unifies the Electrocatalytic Oxygen Evolution Performance of Nonstoichiometric Mixed Metal Oxides". United States. https://doi.org/10.1021/jacsau.1c00359.
@article{osti_1829179,
title = {Dynamic Surface Reconstruction Unifies the Electrocatalytic Oxygen Evolution Performance of Nonstoichiometric Mixed Metal Oxides},
author = {Samira, Samji and Hong, Jiyun and Camayang, John Carl A. and Sun, Kai and Hoffman, Adam S. and Bare, Simon R. and Nikolla, Eranda},
abstractNote = {Compositionally versatile, nonstoichiometric, mixed ionic–electronic conducting metal oxides of the form An+1BnO3n+1 (n = 1 → ∞; A = rare-earth-/alkaline-earth-metal cation; B = transition-metal (TM) cation) remain a highly attractive class of electrocatalysts for catalyzing the energy-intensive oxygen evolution reaction (OER). The current design strategies for describing their OER activities are largely derived assuming a static, unchanged view of their surfaces, despite reports of dynamic structural changes to 3d TM-based perovskites during OER. Herein, through variations in the A- and B-site compositions of An+1BnO3n+1 oxides (n = 1 (A2BO4) or n = ∞ (ABO3); A = La, Sr, Ca; B = Mn, Fe, Co, Ni), we show that, in the absence of electrolyte impurities, surface restructuring is universally the source of high OER activity in these oxides and is dependent on the initial oxide composition. Oxide surface restructuring is induced by irreversible A-site cation dissolution, resulting in in situ formation of a TM oxyhydroxide shell on top of the parent oxide core that serves as the active surface for OER. The rate of surface restructuring is found to depend on (i) composition of A-site cations, with alkaline-earth-metal cations dominating lanthanide cation dissolution, (ii) oxide crystal phase, with n = 1 A2BO4 oxides exhibiting higher rates of A-site dissolution in comparison to n = ∞ ABO3 perovskites, (iii) lattice strain in the oxide induced by mixed rare-earth- and alkaline-earth-metal cations in the A-site, and (iv) oxide reducibility. Among the in situ generated 3d TM oxyhydroxide structures from An+1BnO3n+1 oxides, Co-based structures are characterized by superior OER activity and stability, even in comparison to as-synthesized Co-oxyhydroxide, pointing to the generation of high active surface area structures through oxide restructuring. These insights are critical toward the development of revised design criteria to include surface dynamics for effectively describing the OER activity of nonstoichiometric mixed-metal oxides.},
doi = {10.1021/jacsau.1c00359},
journal = {JACS Au},
number = 12,
volume = 1,
place = {United States},
year = {2021},
month = {11}
}
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/jacsau.1c00359
https://doi.org/10.1021/jacsau.1c00359
Other availability
Search WorldCat to find libraries that may hold this journal
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:
In situ XAS study of CoB i modified hematite photoanodes
journal, January 2017
- Xi, Lifei; Schwanke, Christoph; Zhou, Dong
- Dalton Transactions, Vol. 46, Issue 45
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005
- Ravel, B.; Newville, M.
- Journal of Synchrotron Radiation, Vol. 12, Issue 4
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
The Nature of the Long-Lived Excited State in a Ni II Phthalocyanine Complex Investigated by X-Ray Transient Absorption Spectroscopy
journal, July 2018
- Hong, Jiyun; Kelley, Matthew S.; Shelby, Megan L.
- ChemSusChem, Vol. 11, Issue 14
Design Strategies for Efficient Nonstoichiometric Mixed Metal Oxide Electrocatalysts: Correlating Measurable Oxide Properties to Electrocatalytic Performance
journal, September 2019
- Samira, Samji; Gu, Xiang-Kui; Nikolla, Eranda
- ACS Catalysis, Vol. 9, Issue 11
Recommended Practices and Benchmark Activity for Hydrogen and Oxygen Electrocatalysis in Water Splitting and Fuel Cells
journal, December 2018
- Wei, Chao; Rao, Reshma R.; Peng, Jiayu
- Advanced Materials, Vol. 31, Issue 31
Challenges in Determining the Location of Dopants, to Study the Influence of Metal Doping on the Photocatalytic Activities of ZnO Nanopowders
journal, March 2019
- Tsuzuki, Takuya; He, Rongliang; Dodd, Aaron
- Nanomaterials, Vol. 9, Issue 3
Electronic Origin and Kinetic Feasibility of the Lattice Oxygen Participation During the Oxygen Evolution Reaction on Perovskites
journal, March 2018
- Yoo, Jong Suk; Liu, Yusu; Rong, Xi
- The Journal of Physical Chemistry Letters, Vol. 9, Issue 7
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976
- Shannon, R. D.
- Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767
Synthesis and Characterization of Cobalt Hydroxide, Cobalt Oxyhydroxide, and Cobalt Oxide Nanodiscs
journal, November 2009
- Yang, Jing; Liu, Hongwei; Martens, Wayde N.
- The Journal of Physical Chemistry C, Vol. 114, Issue 1
Ruddlesden–Popper perovskites in electrocatalysis
journal, January 2020
- Xu, Xiaomin; Pan, Yangli; Zhong, Yijun
- Materials Horizons, Vol. 7, Issue 10
A strong steric hindrance effect on ground state, excited state, and charge separated state properties of a Cu I -diimine complex captured by X-ray transient absorption spectroscopy
journal, January 2014
- Huang, J.; Mara, M. W.; Stickrath, A. B.
- Dalton Trans., Vol. 43, Issue 47
The Comprehensive Understanding of 10 mA cmgeo−2 as an Evaluation Parameter for Electrochemical Water Splitting
journal, July 2018
- Wei, Chao; Xu, Zhichuan J.
- Small Methods, Vol. 2, Issue 11
The Electrocatalysis of Oxygen Evolution on Perovskites
journal, January 1984
- Bockris, John O'M.
- Journal of The Electrochemical Society, Vol. 131, Issue 2
In-situ structure and catalytic mechanism of NiFe and CoFe layered double hydroxides during oxygen evolution
journal, May 2020
- Dionigi, Fabio; Zeng, Zhenhua; Sinev, Ilya
- Nature Communications, Vol. 11, Issue 1
Highly Accurate Excited-State Structure of [Os(bpy) 2 dcbpy] 2+ Determined by X-ray Transient Absorption Spectroscopy
journal, June 2014
- Zhang, Xiaoyi; Canton, Sophie E.; Smolentsev, Grigory
- Journal of the American Chemical Society, Vol. 136, Issue 24
Efficient Oxygen Electrocatalysis by Nanostructured Mixed-Metal Oxides
journal, May 2018
- Gu, Xiang-Kui; Carneiro, Juliana S. A.; Samira, Samji
- Journal of the American Chemical Society, Vol. 140, Issue 26
Aprotic and Aqueous Li–O2 Batteries
journal, April 2014
- Lu, Jun; Li, Li; Park, Jin-Bum
- Chemical Reviews, Vol. 114, Issue 11, p. 5611-5640
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
Sol-gel preparation and characterization of non-substituted and Sr-substituted lanthanum cobaltates
journal, September 2008
- Cizauskaite, Sigute; Kareiva, Aivaras
- Open Chemistry, Vol. 6, Issue 3
Electronic and crystal structure changes induced by in-plane oxygen vacancies in multiferroic
journal, February 2016
- Cheng, Shaobo; Li, Menglei; Meng, Qingping
- Physical Review B, Vol. 93, Issue 5
Acidic Oxygen Evolution Reaction Activity–Stability Relationships in Ru-Based Pyrochlores
journal, October 2020
- Hubert, McKenzie A.; Patel, Anjli M.; Gallo, Alessandro
- ACS Catalysis, Vol. 10, Issue 20
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
Perovskite Oxide Based Electrodes for the Oxygen Reduction and Evolution Reactions: The Underlying Mechanism
journal, February 2021
- Beall, Casey E.; Fabbri, Emiliana; Schmidt, Thomas J.
- ACS Catalysis, Vol. 11, Issue 5
Dynamic surface self-reconstruction is the key of highly active perovskite nano-electrocatalysts for water splitting
journal, July 2017
- Fabbri, Emiliana; Nachtegaal, Maarten; Binninger, Tobias
- Nature Materials, Vol. 16, Issue 9
Influence of Oxygen Evolution during Water Oxidation on the Surface of Perovskite Oxide Catalysts
journal, October 2012
- May, Kevin J.; Carlton, Christopher E.; Stoerzinger, Kelsey A.
- The Journal of Physical Chemistry Letters, Vol. 3, Issue 22
Exceptional electrocatalytic oxygen evolution via tunable charge transfer interactions in La0.5Sr1.5Ni1−xFexO4±δ Ruddlesden-Popper oxides
journal, August 2018
- Forslund, Robin P.; Hardin, William G.; Rong, Xi
- Nature Communications, Vol. 9, Issue 1
Excited-state molecular structures captured by X-ray transient absorption spectroscopy: a decade and beyond
journal, February 2010
- Chen, Lin X.; Zhang, Xiaoyi; Lockard, Jenny V.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 66, Issue 2
Redox and electrochemical water splitting catalytic properties of hydrated metal oxide modified electrodes
journal, January 2013
- Doyle, Richard L.; Godwin, Ian J.; Brandon, Michael P.
- Physical Chemistry Chemical Physics, Vol. 15, Issue 33
Opportunities and Challenges in Utilizing Metal-Modified Transition Metal Carbides as Low-Cost Electrocatalysts
journal, October 2017
- Tackett, Brian M.; Sheng, Wenchao; Chen, Jingguang G.
- Joule, Vol. 1, Issue 2
Dynamically Stable Active Sites from Surface Evolution of Perovskite Materials during the Oxygen Evolution Reaction
journal, January 2021
- Lopes, Pietro P.; Chung, Dong Young; Rui, Xue
- Journal of the American Chemical Society, Vol. 143, Issue 7
Activating lattice oxygen redox reactions in metal oxides to catalyse oxygen evolution
journal, January 2017
- Grimaud, Alexis; Diaz-Morales, Oscar; Han, Binghong
- Nature Chemistry, Vol. 9, Issue 5
Lattice oxygen redox chemistry in solid-state electrocatalysts for water oxidation
journal, January 2021
- Zhang, Ning; Chai, Yang
- Energy & Environmental Science, Vol. 14, Issue 9
Evidence for Hole-Driven Conductivity in and Thin Films
journal, October 1997
- Ju, H. L.; Sohn, H. -C.; Krishnan, Kannan M.
- Physical Review Letters, Vol. 79, Issue 17
Functional Role of Fe-Doping in Co-Based Perovskite Oxide Catalysts for Oxygen Evolution Reaction
journal, March 2019
- Kim, Bae-Jung; Fabbri, Emiliana; Abbott, Daniel F.
- Journal of the American Chemical Society, Vol. 141, Issue 13
The stability number as a metric for electrocatalyst stability benchmarking
journal, June 2018
- Geiger, Simon; Kasian, Olga; Ledendecker, Marc
- Nature Catalysis, Vol. 1, Issue 7
Nonprecious Metal Catalysts for Tuning Discharge Product Distribution at Solid–Solid Interfaces of Aprotic Li–O 2 Batteries
journal, July 2019
- Samira, Samji; Deshpande, Siddharth; Roberts, Charles A.
- Chemistry of Materials, Vol. 31, Issue 18
Progress and Perspectives of Electrochemical CO 2 Reduction on Copper in Aqueous Electrolyte
journal, April 2019
- Nitopi, Stephanie; Bertheussen, Erlend; Scott, Soren B.
- Chemical Reviews, Vol. 119, Issue 12
Embracing the Complexity of Catalytic Structures: A Viewpoint on the Synthesis of Nonstoichiometric Mixed Metal Oxides for Catalysis
journal, November 2019
- Carneiro, Juliana S. A.; Williams, Jillian; Gryko, Aleksandra
- ACS Catalysis, Vol. 10, Issue 1
Chemical and structural origin of lattice oxygen oxidation in Co–Zn oxyhydroxide oxygen evolution electrocatalysts
journal, March 2019
- Huang, Zhen-Feng; Song, Jiajia; Du, Yonghua
- Nature Energy, Vol. 4, Issue 4
Trends in activity for the water electrolyser reactions on 3d M(Ni,Co,Fe,Mn) hydr(oxy)oxide catalysts
journal, May 2012
- Subbaraman, Ram; Tripkovic, Dusan; Chang, Kee-Chul
- Nature Materials, Vol. 11, Issue 6
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
Rationality in the new oxygen evolution catalyst development
journal, December 2018
- Pittkowski, Rebecca; Krtil, Petr; Rossmeisl, Jan
- Current Opinion in Electrochemistry, Vol. 12
Mechanism of Oxygen Evolution Catalyzed by Cobalt Oxyhydroxide: Cobalt Superoxide Species as a Key Intermediate and Dioxygen Release as a Rate-Determining Step
journal, June 2020
- Moysiadou, Aliki; Lee, Seunghwa; Hsu, Chia-Shuo
- Journal of the American Chemical Society, Vol. 142, Issue 27
Molecular Insight in Structure and Activity of Highly Efficient, Low-Ir Ir–Ni Oxide Catalysts for Electrochemical Water Splitting (OER)
journal, September 2015
- Reier, Tobias; Pawolek, Zarina; Cherevko, Serhiy
- Journal of the American Chemical Society, Vol. 137, Issue 40
Aprotic Alkali Metal–O 2 Batteries: Role of Cathode Surface-Mediated Processes and Heterogeneous Electrocatalysis
journal, January 2021
- Samira, Samji; Deshpande, Siddharth; Greeley, Jeffrey
- ACS Energy Letters, Vol. 6, Issue 2
The Catalysis of the Oxygen Evolution Reaction by Iron Impurities in Thin Film Nickel Oxide Electrodes
journal, January 1987
- Corrigan, Dennis A.
- Journal of The Electrochemical Society, Vol. 134, Issue 2
NiFe-Based (Oxy)hydroxide Catalysts for Oxygen Evolution Reaction in Non-Acidic Electrolytes
journal, July 2016
- Dionigi, Fabio; Strasser, Peter
- Advanced Energy Materials, Vol. 6, Issue 23
Benchmarking Heterogeneous Electrocatalysts for the Oxygen Evolution Reaction
journal, October 2013
- McCrory, Charles C. L.; Jung, Suho; Peters, Jonas C.
- Journal of the American Chemical Society, Vol. 135, Issue 45
Oxygen Evolution Reaction Electrocatalysis on Transition Metal Oxides and (Oxy)hydroxides: Activity Trends and Design Principles
journal, October 2015
- Burke, Michaela S.; Enman, Lisa J.; Batchellor, Adam S.
- Chemistry of Materials, Vol. 27, Issue 22
Reactive Fe-Sites in Ni/Fe (Oxy)hydroxide Are Responsible for Exceptional Oxygen Electrocatalysis Activity
journal, August 2017
- Stevens, Michaela Burke; Trang, Christina D. M.; Enman, Lisa J.
- Journal of the American Chemical Society, Vol. 139, Issue 33
Spin and orbital states in single-layered La Ca CoO studied by doping- and temperature-dependent near-edge x-ray absorption fine structure
journal, July 2011
- Merz, M.; Fuchs, D.; Assmann, A.
- Physical Review B, Vol. 84, Issue 1
Activity of pure and transition metal-modified CoOOH for the oxygen evolution reaction in an alkaline medium
journal, January 2017
- Chen, Zhu; Kronawitter, Coleman X.; Yeh, Yao-Wen
- Journal of Materials Chemistry A, Vol. 5, Issue 2
Nickel–Iron Oxyhydroxide Oxygen-Evolution Electrocatalysts: The Role of Intentional and Incidental Iron Incorporation
journal, April 2014
- Trotochaud, Lena; Young, Samantha L.; Ranney, James K.
- Journal of the American Chemical Society, Vol. 136, Issue 18
Oxygen evolution electrocatalysis using mixed metal oxides under acidic conditions: Challenges and opportunities
journal, August 2020
- Gu, Xiang-Kui; Camayang, John Carl A.; Samira, Samji
- Journal of Catalysis, Vol. 388
Design Principles for Efficient and Stable Water Splitting Photoelectrocatalysts
journal, April 2021
- Hemmerling, John R.; Mathur, Aarti; Linic, Suljo
- Accounts of Chemical Research, Vol. 54, Issue 8
Oxygen evolution on Ru1 − x Ni x O2 − y nanocrystalline electrodes
journal, August 2008
- Macounová, Kateřina; Jirkovský, Jakub; Makarova, Marina V.
- Journal of Solid State Electrochemistry, Vol. 13, Issue 6
Modulating Catalytic Properties of Targeted Metal Cationic Centers in Nonstochiometric Mixed Metal Oxides for Electrochemical Oxygen Reduction
journal, February 2021
- Samira, Samji; Camayang, John Carl A.; Patel, Krishna
- ACS Energy Letters, Vol. 6, Issue 3
In-Situ X-ray Absorption Spectroscopic Study on Variation of Electronic Transitions and Local Structure of LiNi 1/3 Co 1/3 Mn 1/3 O 2 Cathode Material during Electrochemical Cycling
journal, June 2005
- Tsai, Y. W.; Hwang, B. J.; Ceder, G.
- Chemistry of Materials, Vol. 17, Issue 12
Structural and Electronic Engineering of Ir-Doped Ni-(Oxy)hydroxide Nanosheets for Enhanced Oxygen Evolution Activity
journal, April 2021
- Liu, Jinlong; Xiao, Juanxiu; Wang, Zhenyu
- ACS Catalysis, Vol. 11, Issue 9
Dynamic stability of active sites in hydr(oxy)oxides for the oxygen evolution reaction
journal, March 2020
- Chung, Dong Young; Lopes, Pietro P.; Farinazzo Bergamo Dias Martins, Pedro
- Nature Energy, Vol. 5, Issue 3
Recent Progress on Multimetal Oxide Catalysts for the Oxygen Evolution Reaction
journal, January 2018
- Kim, Ju Seong; Kim, Byunghoon; Kim, Hyunah
- Advanced Energy Materials, Vol. 8, Issue 11
Role of Lattice Oxygen Participation in Understanding Trends in the Oxygen Evolution Reaction on Perovskites
journal, April 2018
- Yoo, Jong Suk; Rong, Xi; Liu, Yusu
- ACS Catalysis, Vol. 8, Issue 5
Electrochemical oxygen reduction on layered mixed metal oxides: Effect of B-site substitution
journal, January 2019
- Samira, Samji; Camayang, John Carl A.; Nacy, Ayad M.
- Journal of Electroanalytical Chemistry, Vol. 833