Operando X‐Ray Absorption Spectroscopy Shows Iron Oxidation Is Concurrent with Oxygen Evolution in Cobalt–Iron (Oxy)hydroxide Electrocatalysts
Abstract
Abstract Iron cations are essential for the high activity of nickel and cobalt‐based (oxy)hydroxides for the oxygen evolution reaction, but the role of iron in the catalytic mechanism remains under active investigation. Operando X‐ray absorption spectroscopy and density functional theory calculations are used to demonstrate partial Fe oxidation and a shortening of the Fe−O bond length during oxygen evolution on Co(Fe)O x H y . Cobalt oxidation during oxygen evolution is only observed in the absence of iron. These results demonstrate a different mechanism for water oxidation in the presence and absence of iron and support the hypothesis that oxidized iron species are involved in water‐oxidation catalysis on Co(Fe)O x H y .
- Authors:
-
- Department of Chemistry &, Biochemistry and the Materials Science Institute University of Oregon Eugene OR 97403 USA
- Department of Materials Science &, Engineering and The Nancy &, Stephen Grand Technion Energy Program Technion—Israel Institute of Technology Haifa 3200003 Israel
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1468491
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Angewandte Chemie
- Additional Journal Information:
- Journal Name: Angewandte Chemie Journal Volume: 130 Journal Issue: 39; Journal ID: ISSN 0044-8249
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Enman, Lisa J., Stevens, Michaela Burke, Dahan, Meir Haim, Nellist, Michael R., Toroker, Maytal Caspary, and Boettcher, Shannon W.. Operando X‐Ray Absorption Spectroscopy Shows Iron Oxidation Is Concurrent with Oxygen Evolution in Cobalt–Iron (Oxy)hydroxide Electrocatalysts. Germany: N. p., 2018.
Web. doi:10.1002/ange.201808818.
Enman, Lisa J., Stevens, Michaela Burke, Dahan, Meir Haim, Nellist, Michael R., Toroker, Maytal Caspary, & Boettcher, Shannon W.. Operando X‐Ray Absorption Spectroscopy Shows Iron Oxidation Is Concurrent with Oxygen Evolution in Cobalt–Iron (Oxy)hydroxide Electrocatalysts. Germany. https://doi.org/10.1002/ange.201808818
Enman, Lisa J., Stevens, Michaela Burke, Dahan, Meir Haim, Nellist, Michael R., Toroker, Maytal Caspary, and Boettcher, Shannon W.. Tue .
"Operando X‐Ray Absorption Spectroscopy Shows Iron Oxidation Is Concurrent with Oxygen Evolution in Cobalt–Iron (Oxy)hydroxide Electrocatalysts". Germany. https://doi.org/10.1002/ange.201808818.
@article{osti_1468491,
title = {Operando X‐Ray Absorption Spectroscopy Shows Iron Oxidation Is Concurrent with Oxygen Evolution in Cobalt–Iron (Oxy)hydroxide Electrocatalysts},
author = {Enman, Lisa J. and Stevens, Michaela Burke and Dahan, Meir Haim and Nellist, Michael R. and Toroker, Maytal Caspary and Boettcher, Shannon W.},
abstractNote = {Abstract Iron cations are essential for the high activity of nickel and cobalt‐based (oxy)hydroxides for the oxygen evolution reaction, but the role of iron in the catalytic mechanism remains under active investigation. Operando X‐ray absorption spectroscopy and density functional theory calculations are used to demonstrate partial Fe oxidation and a shortening of the Fe−O bond length during oxygen evolution on Co(Fe)O x H y . Cobalt oxidation during oxygen evolution is only observed in the absence of iron. These results demonstrate a different mechanism for water oxidation in the presence and absence of iron and support the hypothesis that oxidized iron species are involved in water‐oxidation catalysis on Co(Fe)O x H y .},
doi = {10.1002/ange.201808818},
journal = {Angewandte Chemie},
number = 39,
volume = 130,
place = {Germany},
year = {Tue Sep 04 00:00:00 EDT 2018},
month = {Tue Sep 04 00:00:00 EDT 2018}
}
https://doi.org/10.1002/ange.201808818
Works referenced in this record:
Operando Analysis of NiFe and Fe Oxyhydroxide Electrocatalysts for Water Oxidation: Detection of Fe 4+ by Mössbauer Spectroscopy
journal, November 2015
- Chen, Jamie Y. C.; Dang, Lianna; Liang, Hanfeng
- Journal of the American Chemical Society, Vol. 137, Issue 48
EPR Evidence for Co(IV) Species Produced During Water Oxidation at Neutral pH
journal, May 2010
- McAlpin, J. Gregory; Surendranath, Yogesh; Dincǎ, Mircea
- Journal of the American Chemical Society, Vol. 132, Issue 20
On the chemical state of Co oxide electrocatalysts during alkaline water splitting
journal, January 2013
- Friebel, Daniel; Bajdich, Michal; Yeo, Boon Siang
- Physical Chemistry Chemical Physics, Vol. 15, Issue 40
X-ray Spectroscopic Characterization of Co(IV) and Metal–Metal Interactions in Co 4 O 4 : Electronic Structure Contributions to the Formation of High-Valent States Relevant to the Oxygen Evolution Reaction
journal, August 2016
- Hadt, Ryan G.; Hayes, Dugan; Brodsky, Casey N.
- Journal of the American Chemical Society, Vol. 138, Issue 34
Revised Oxygen Evolution Reaction Activity Trends for First-Row Transition-Metal (Oxy)hydroxides in Alkaline Media
journal, August 2015
- Burke, Michaela S.; Zou, Shihui; Enman, Lisa J.
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 18
Self-healing catalysis in water
journal, September 2017
- Costentin, Cyrille; Nocera, Daniel G.
- Proceedings of the National Academy of Sciences, Vol. 114, Issue 51
Spectroscopic identification of active sites for the oxygen evolution reaction on iron-cobalt oxides
journal, December 2017
- Smith, Rodney D. L.; Pasquini, Chiara; Loos, Stefan
- Nature Communications, Vol. 8, Issue 1
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
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
Tracking Catalyst Redox States and Reaction Dynamics in Ni–Fe Oxyhydroxide Oxygen Evolution Reaction Electrocatalysts: The Role of Catalyst Support and Electrolyte pH
journal, January 2017
- Görlin, Mikaela; Ferreira de Araújo, Jorge; Schmies, Henrike
- Journal of the American Chemical Society, Vol. 139, Issue 5
Molybdenum x-ray absorption edge spectra. The chemical state of molybdenum in nitrogenase
journal, March 1976
- Cramer, S. P.; Eccles, T. K.; Kutzler, F. W.
- Journal of the American Chemical Society, Vol. 98, Issue 5
Nickel-iron catalysts for electrochemical water oxidation – redox synergism investigated by in situ X-ray spectroscopy with millisecond time resolution
journal, January 2018
- González-Flores, Diego; Klingan, Katharina; Chernev, Petko
- Sustainable Energy & Fuels, Vol. 2, Issue 9
Time-resolved observations of water oxidation intermediates on a cobalt oxide nanoparticle catalyst
journal, February 2014
- Zhang, Miao; de Respinis, Moreno; Frei, Heinz
- Nature Chemistry, Vol. 6, Issue 4
Mechanistic Studies of the Oxygen Evolution Reaction by a Cobalt-Phosphate Catalyst at Neutral pH
journal, November 2010
- Surendranath, Yogesh; Kanan, Matthew W.; Nocera, Daniel G.
- Journal of the American Chemical Society, Vol. 132, Issue 46
Enhanced Catalysis of the Electrochemical Oxygen Evolution Reaction by Iron(III) Ions Adsorbed on Amorphous Cobalt Oxide
journal, December 2017
- Gong, Luo; Chng, Xin Yu Esther; Du, Yonghua
- ACS Catalysis, Vol. 8, Issue 2
Characterization of and as a function of temperature by x-ray absorption spectroscopy
journal, March 2006
- Deb, Aniruddha; Ralph, James M.; Cairns, Elton J.
- Physical Review B, Vol. 73, Issue 11
Exfoliation of layered double hydroxides for enhanced oxygen evolution catalysis
journal, July 2014
- Song, Fang; Hu, Xile
- Nature Communications, Vol. 5, Issue 1
Hydrogen Bonds of gamma-FeOOH.
journal, January 1978
- Christensen, Henrik; Christensen, A. Nørlund; Turpeinen, Urho
- Acta Chemica Scandinavica, Vol. 32a
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998
- Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
- Physical Review B, Vol. 57, Issue 3, p. 1505-1509
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011
- Momma, Koichi; Izumi, Fujio
- Journal of Applied Crystallography, Vol. 44, Issue 6
Trapping an Iron(VI) Water-Splitting Intermediate in Nonaqueous Media
journal, April 2018
- Hunter, Bryan M.; Thompson, Niklas B.; Müller, Astrid M.
- Joule, Vol. 2, Issue 4
Oxygen Evolution Reaction Dynamics, Faradaic Charge Efficiency, and the Active Metal Redox States of Ni–Fe Oxide Water Splitting Electrocatalysts
journal, April 2016
- Görlin, Mikaela; Chernev, Petko; Ferreira de Araújo, Jorge
- Journal of the American Chemical Society, Vol. 138, Issue 17
Identification of Highly Active Fe Sites in (Ni,Fe)OOH for Electrocatalytic Water Splitting
journal, January 2015
- Friebel, Daniel; Louie, Mary W.; Bajdich, Michal
- Journal of the American Chemical Society, Vol. 137, Issue 3
Cobalt–Iron (Oxy)hydroxide Oxygen Evolution Electrocatalysts: The Role of Structure and Composition on Activity, Stability, and Mechanism
journal, March 2015
- Burke, Michaela S.; Kast, Matthew G.; Trotochaud, Lena
- Journal of the American Chemical Society, Vol. 137, Issue 10
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
Edge reactivity and water-assisted dissociation on cobalt oxide nanoislands
journal, January 2017
- Fester, J.; García-Melchor, M.; Walton, A. S.
- Nature Communications, Vol. 8, Issue 1
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
Understanding the Oxygen Evolution Reaction Mechanism on CoO x using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy
journal, June 2017
- Favaro, Marco; Yang, Jinhui; Nappini, Silvia
- Journal of the American Chemical Society, Vol. 139, Issue 26
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
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
Charge-Transfer Effects in Ni–Fe and Ni–Fe–Co Mixed-Metal Oxides for the Alkaline Oxygen Evolution Reaction
journal, December 2015
- Bates, Michael K.; Jia, Qingying; Doan, Huong
- ACS Catalysis, Vol. 6, Issue 1
Iron Is the Active Site in Nickel/Iron Water Oxidation Electrocatalysts
journal, April 2018
- Hunter, Bryan; Winkler, Jay; Gray, Harry
- Molecules, Vol. 23, Issue 4
Lateral-Size-Mediated Efficient Oxygen Evolution Reaction: Insights into the Atomically Thin Quantum Dot Structure of NiFe 2 O 4
journal, July 2017
- Yang, Haidong; Liu, Yang; Luo, Sha
- ACS Catalysis, Vol. 7, Issue 8
Charge disproportionation in probed by diffraction and spectroscopic experiments
journal, February 2008
- Blasco, Javier; Aznar, Bartolomé; García, Joaquín
- Physical Review B, Vol. 77, Issue 5
Insights into the durability of Co–Fe spinel oxygen evolution electrocatalysts via operando studies of the catalyst structure
journal, January 2018
- Calvillo, L.; Carraro, F.; Vozniuk, O.
- Journal of Materials Chemistry A, Vol. 6, Issue 16
Characterization of NiFe oxyhydroxide electrocatalysts by integrated electronic structure calculations and spectroelectrochemistry
journal, March 2017
- Goldsmith, Zachary K.; Harshan, Aparna K.; Gerken, James B.
- Proceedings of the National Academy of Sciences, Vol. 114, Issue 12
Solution-Cast Metal Oxide Thin Film Electrocatalysts for Oxygen Evolution
journal, October 2012
- Trotochaud, Lena; Ranney, James K.; Williams, Kerisha N.
- Journal of the American Chemical Society, Vol. 134, Issue 41
X-ray Absorption Spectroscopy Studies of the Local Atomic and Electronic Structure of Iron Incorporated into Electrodeposited Hydrous Nickel Oxide Films †
journal, May 2000
- Balasubramanian, M.; Melendres, C. A.; Mini, S.
- The Journal of Physical Chemistry B, Vol. 104, Issue 18
Influence of iron doping on tetravalent nickel content in catalytic oxygen evolving films
journal, January 2017
- Li, Nancy; Bediako, D. Kwabena; Hadt, Ryan G.
- Proceedings of the National Academy of Sciences, Vol. 114, Issue 7
The secret behind the success of doping nickel oxyhydroxide with iron
journal, January 2017
- Fidelsky, Vicky; Toroker, Maytal Caspary
- Phys. Chem. Chem. Phys., Vol. 19, Issue 11