Theoretical Investigation of the Activity of Cobalt Oxides for the Electrochemical Oxidation of Water
Abstract
The presence of layered cobalt oxides has been identified experimentally in Co-based anodes under oxygen-evolving conditions. In this work, we report the results of theoretical investigations of the relative stability of layered and spinel bulk phases of Co oxides, as well as the stability of selected surfaces as a function of applied potential and pH. We then study the oxygen evolution reaction (OER) on these surfaces and obtain activity trends at experimentally relevant electro-chemical conditions. Our calculated volume Pourbaix diagram shows that β-CoOOH is the active phase where the OER occurs in alkaline media. We calculate relative surface stabilities and adsorbate coverages of the most stable low-index surfaces of β-CoOOH: (0001), ($$01\bar{12}$$), and ($$10\bar{14}$$). We find that at low applied potentials, the ($$10\bar{14}$$) surface is the most stable, while the ($$01\bar{12}$$) surface is the more stable at higher potentials. Next, we compare the theoretical overpotentials for all three surfaces and find that the ($$10\bar{14}$$) surface is the most active one as characteried by an overpotential of η = 0.48 V. The high activity of the ($$10\bar{14}$$) surface can be attributed to the observation that the resting state of Co in the active site is Co3+ during the OER, whereas Co is in the Co4+ state in the less active surfaces. Lastly, we demonstrate that the overpotential of the ($$10\bar{14}$$) surface can be lowered further by surface substitution of Co by Ni. This finding could explain the experimentally observed enhancement in the OER activity of NiyCo1-yOx thin films with increasing Ni content. All energetics in this work were obtained from density functional theory using the Hubbard-U correction.
- Authors:
-
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
- Stanford Univ., Stanford, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences & Biosciences Division (SC-22.1)
- OSTI Identifier:
- 1511371
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 135; Journal Issue: 36; 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; adsorption; free energy; oxides; radiology; surface energy
Citation Formats
Bajdich, Michal, García-Mota, Mónica, Vojvodic, Aleksandra, Nørskov, Jens K., and Bell, Alexis T. Theoretical Investigation of the Activity of Cobalt Oxides for the Electrochemical Oxidation of Water. United States: N. p., 2013.
Web. doi:10.1021/ja405997s.
Bajdich, Michal, García-Mota, Mónica, Vojvodic, Aleksandra, Nørskov, Jens K., & Bell, Alexis T. Theoretical Investigation of the Activity of Cobalt Oxides for the Electrochemical Oxidation of Water. United States. https://doi.org/10.1021/ja405997s
Bajdich, Michal, García-Mota, Mónica, Vojvodic, Aleksandra, Nørskov, Jens K., and Bell, Alexis T. Wed .
"Theoretical Investigation of the Activity of Cobalt Oxides for the Electrochemical Oxidation of Water". United States. https://doi.org/10.1021/ja405997s. https://www.osti.gov/servlets/purl/1511371.
@article{osti_1511371,
title = {Theoretical Investigation of the Activity of Cobalt Oxides for the Electrochemical Oxidation of Water},
author = {Bajdich, Michal and García-Mota, Mónica and Vojvodic, Aleksandra and Nørskov, Jens K. and Bell, Alexis T.},
abstractNote = {The presence of layered cobalt oxides has been identified experimentally in Co-based anodes under oxygen-evolving conditions. In this work, we report the results of theoretical investigations of the relative stability of layered and spinel bulk phases of Co oxides, as well as the stability of selected surfaces as a function of applied potential and pH. We then study the oxygen evolution reaction (OER) on these surfaces and obtain activity trends at experimentally relevant electro-chemical conditions. Our calculated volume Pourbaix diagram shows that β-CoOOH is the active phase where the OER occurs in alkaline media. We calculate relative surface stabilities and adsorbate coverages of the most stable low-index surfaces of β-CoOOH: (0001), ($01\bar{12}$), and ($10\bar{14}$). We find that at low applied potentials, the ($10\bar{14}$) surface is the most stable, while the ($01\bar{12}$) surface is the more stable at higher potentials. Next, we compare the theoretical overpotentials for all three surfaces and find that the ($10\bar{14}$) surface is the most active one as characteried by an overpotential of η = 0.48 V. The high activity of the ($10\bar{14}$) surface can be attributed to the observation that the resting state of Co in the active site is Co3+ during the OER, whereas Co is in the Co4+ state in the less active surfaces. Lastly, we demonstrate that the overpotential of the ($10\bar{14}$) surface can be lowered further by surface substitution of Co by Ni. This finding could explain the experimentally observed enhancement in the OER activity of NiyCo1-yOx thin films with increasing Ni content. All energetics in this work were obtained from density functional theory using the Hubbard-U correction.},
doi = {10.1021/ja405997s},
journal = {Journal of the American Chemical Society},
number = 36,
volume = 135,
place = {United States},
year = {Wed Aug 14 00:00:00 EDT 2013},
month = {Wed Aug 14 00:00:00 EDT 2013}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 920 works
Citation information provided by
Web of Science
Web of Science
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:
Prediction of solid-aqueous equilibria: Scheme to combine first-principles calculations of solids with experimental aqueous states
journal, June 2012
- Persson, Kristin A.; Waldwick, Bryn; Lazic, Predrag
- Physical Review B, Vol. 85, Issue 23
Tailoring the Morphology of LiCoO 2 : A First Principles Study
journal, August 2009
- Kramer, Denis; Ceder, Gerbrand
- Chemistry of Materials, Vol. 21, Issue 16
The structure of cobalt oxide, Co 3 O 4
journal, February 1973
- Smith, W. L.; Hobson, A. D.
- Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 29, Issue 2
A comparative study of the oxygen evolution reaction on oxidised nickel, cobalt and iron electrodes in base
journal, March 2010
- Lyons, Michael E. G.; Brandon, Michael P.
- Journal of Electroanalytical Chemistry, Vol. 641, Issue 1-2
Universality in Heterogeneous Catalysis
journal, July 2002
- Nørskov, J. K.; Bligaard, T.; Logadottir, A.
- Journal of Catalysis, Vol. 209, Issue 2
Anodically electrodeposited Co+Ni mixed oxide electrode: preparation and electrocatalytic activity for oxygen evolution in alkaline media
journal, October 2004
- Wu, Gang; Li, Ning; Zhou, De-Rui
- Journal of Solid State Chemistry, Vol. 177, Issue 10, p. 3682-3692
X-Ray Determination of Electron-Density Distributions in Oxides, MgO, MnO, CoO, and NiO, and Atomic Scattering Factors of their Constituent Atoms
journal, January 1979
- Sasaki, Satoshi; Fujino, Kiyoshi; TakÉUchi, Yoshio
- Proceedings of the Japan Academy. Ser. B: Physical and Biological Sciences, Vol. 55, Issue 2
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Calibration of the DFT/GGA+U Method for Determination of Reduction Energies for Transition and Rare Earth Metal Oxides of Ti, V, Mo, and Ce
journal, June 2011
- Lutfalla, Suzanne; Shapovalov, Vladimir; Bell, Alexis T.
- Journal of Chemical Theory and Computation, Vol. 7, Issue 7
First-principles prediction of redox potentials in transition-metal compounds with
journal, December 2004
- Zhou, F.; Cococcioni, M.; Marianetti, C. A.
- Physical Review B, Vol. 70, Issue 23
Thermodynamic theory of multi-electron transfer reactions: Implications for electrocatalysis
journal, September 2011
- Koper, Marc T. M.
- Journal of Electroanalytical Chemistry, Vol. 660, Issue 2
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
Oxygen evolution reaction on NixCo(3—xO4 electrodes with spinel structure
journal, October 1993
- De Chialvo, M. R. Gennero; Chialvo, A. C.
- Electrochimica Acta, Vol. 38, Issue 15
Periodic density functional study of Co3O4 surfaces
journal, January 2011
- Montoya, Alejandro; Haynes, Brian S.
- Chemical Physics Letters, Vol. 502, Issue 1-3
Thermodynamic stability of CoOOH and its coprecipitation with manganese
journal, March 1985
- Hem, John D.; Roberson, Charles E.; Lind, Carol J.
- Geochimica et Cosmochimica Acta, Vol. 49, Issue 3
CoO2, The End Member of the LixCoO2 Solid Solution
journal, January 1996
- Amatucci, G. G.; Tarascon, J. M.; Klein, L. C.
- Journal of The Electrochemical Society, Vol. 143, Issue 3, p. 1114-1123
Solar Water Splitting Cells
journal, November 2010
- Walter, Michael G.; Warren, Emily L.; McKone, James R.
- Chemical Reviews, Vol. 110, Issue 11, p. 6446-6473
Crystal shapes and phase equilibria: A common mathematical basis
journal, June 1996
- Cahn, J. W.; Carter, W. C.
- Metallurgical and Materials Transactions A, Vol. 27, Issue 6
In Situ Formation of an Oxygen-Evolving Catalyst in Neutral Water Containing Phosphate and Co2+
journal, August 2008
- Kanan, M. W.; Nocera, D. G.
- Science, Vol. 321, Issue 5892, p. 1072-1075
Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds
journal, November 2010
- Cook, Timothy R.; Dogutan, Dilek K.; Reece, Steven Y.
- Chemical Reviews, Vol. 110, Issue 11
Impact on electronic correlations on the structural stability, magnetism, and voltage of battery
journal, June 2004
- Bacq, O. Le; Pasturel, A.; Bengone, O.
- Physical Review B, Vol. 69, Issue 24
Wulffman: A tool for the calculation and display of crystal shapes
journal, March 1998
- Roosen, Andrew R.; McCormack, Ryan P.; Carter, W. Craig
- Computational Materials Science, Vol. 11, Issue 1
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
Electrolysis of water on (oxidized) metal surfaces
journal, December 2005
- Rossmeisl, J.; Logadottir, A.; Nørskov, J. K.
- Chemical Physics, Vol. 319, Issue 1-3, p. 178-184
An object-oriented scripting interface to a legacy electronic structure code
journal, January 2002
- Bahn, S. R.; Jacobsen, K. W.
- Computing in Science & Engineering, Vol. 4, Issue 3
Enhanced Activity of Gold-Supported Cobalt Oxide for the Electrochemical Evolution of Oxygen
journal, April 2011
- Yeo, Boon Siang; Bell, Alexis T.
- Journal of the American Chemical Society, Vol. 133, Issue 14
Composition, structure, and stability of as a function of oxygen pressure
journal, December 2001
- Reuter, Karsten; Scheffler, Matthias
- Physical Review B, Vol. 65, Issue 3
Linear response approach to the calculation of the effective interaction parameters in the method
journal, January 2005
- Cococcioni, Matteo; de Gironcoli, Stefano
- Physical Review B, Vol. 71, Issue 3
Structural, electronic, and magnetic properties of a ferromagnetic semiconductor: Co-dopedTiO 2
journal, September 2003
- Geng, W. T.; Kim, Kwang S.
- Physical Review B, Vol. 68, Issue 12
Tailoring the Activity for Oxygen Evolution Electrocatalysis on Rutile TiO2(110) by Transition-Metal Substitution
journal, August 2011
- García-Mota, Mónica; Vojvodic, Aleksandra; Metiu, Horia
- ChemCatChem, Vol. 3, Issue 10
Water Oxidation on Pure and Doped Hematite (0001) Surfaces: Prediction of Co and Ni as Effective Dopants for Electrocatalysis
journal, August 2012
- Liao, Peilin; Keith, John A.; Carter, Emily A.
- Journal of the American Chemical Society, Vol. 134, Issue 32
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
Rotationally invariant ab initio evaluation of Coulomb and exchange parameters for DFT+U calculations
journal, July 2008
- Mosey, Nicholas J.; Liao, Peilin; Carter, Emily A.
- The Journal of Chemical Physics, Vol. 129, Issue 1
Electrolysis of water on oxide surfaces
journal, September 2007
- Rossmeisl, J.; Qu, Z. -W.; Zhu, H.
- Journal of Electroanalytical Chemistry, Vol. 607, Issue 1-2
New insight in the behaviour of Co–H2O system at 25–150°C, based on revised Pourbaix diagrams
journal, January 2008
- Chivot, J.; Mendoza, L.; Mansour, C.
- Corrosion Science, Vol. 50, Issue 1
Electronic states and magnetic structure at the Co O (110) surface: A first-principles study
journal, February 2012
- Chen, Jia; Selloni, Annabella
- Physical Review B, Vol. 85, Issue 8
Importance of Correlation in Determining Electrocatalytic Oxygen Evolution Activity on Cobalt Oxides
journal, September 2012
- García-Mota, Mónica; Bajdich, Michal; Viswanathan, Venkatasubramanian
- The Journal of Physical Chemistry C, Vol. 116, Issue 39
Oxidation and Photo-Oxidation of Water on TiO 2 Surface
journal, June 2008
- Valdés, Á.; Qu, Z. -W.; Kroes, G. -J.
- The Journal of Physical Chemistry C, Vol. 112, Issue 26
Zur kenntnis der nickelhydroxidelektrode—I.Über das nickel (II)-hydroxidhydrat
journal, August 1966
- Bode, H.; Dehmelt, K.; Witte, J.
- Electrochimica Acta, Vol. 11, Issue 8
Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals
journal, March 1999
- Hammer, B.; Hansen, L. B.; Nørskov, J. K.
- Physical Review B, Vol. 59, Issue 11
Band theory and Mott insulators: Hubbard U instead of Stoner I
journal, July 1991
- Anisimov, Vladimir I.; Zaanen, Jan; Andersen, Ole K.
- Physical Review B, Vol. 44, Issue 3, p. 943-954
Cluster Study of the Photo-Oxidation of Water on Rutile Titanium Dioxide (TiO 2 )
journal, January 2010
- Valdés, Á.; Kroes, G. -J.
- The Journal of Physical Chemistry C, Vol. 114, Issue 3
Solar hydrogen production with semiconductor metal oxides: new directions in experiment and theory
journal, January 2012
- Valdés, Álvaro; Brillet, Jeremie; Grätzel, Michael
- Phys. Chem. Chem. Phys., Vol. 14, Issue 1
Formation enthalpies by mixing GGA and GGA calculations
journal, July 2011
- Jain, Anubhav; Hautier, Geoffroy; Ong, Shyue Ping
- Physical Review B, Vol. 84, Issue 4
Crystal structure of brucite-type cobalt hydroxide β-Co{O(H,D)}2 — neutron diffraction, IR and Raman spectroscopy
journal, February 1998
- Mockenhaupt, Ch.; Zeiske, Th.; Lutz, H. D.
- Journal of Molecular Structure, Vol. 443, Issue 1-3
Electrochemical chlorine evolution at rutile oxide (110) surfaces
journal, January 2010
- Hansen, Heine A.; Man, Isabela C.; Studt, Felix
- Phys. Chem. Chem. Phys., Vol. 12, Issue 1
Density functional studies of functionalized graphitic materials with late transition metals for oxygen reduction reactions
journal, January 2011
- Calle-Vallejo, Federico; Martínez, José Ignacio; Rossmeisl, Jan
- Physical Chemistry Chemical Physics, Vol. 13, Issue 34
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
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
Electrocatalytic properties of transition metal oxides for oxygen evolution reaction
journal, May 1986
- Matsumoto, Y.; Sato, E.
- Materials Chemistry and Physics, Vol. 14, Issue 5, p. 397-426
Diffraction and Spectroscopic Studies of the Cobaltic Acid System HCoC 2 –DCoO 2
journal, March 1969
- Delaplane, Robert G.; Ibers, James A.; Ferraro, John R.
- The Journal of Chemical Physics, Vol. 50, Issue 5
Electronic structure and bonding properties of cobalt oxide in the spinel structure
journal, June 2011
- Chen, Jia; Wu, Xifan; Selloni, Annabella
- Physical Review B, Vol. 83, Issue 24
Co3O4 and Co- Based Spinel Oxides Bifunctional Oxygen Electrodes
journal, April 2010
- Hamdani, M.; Singh, R. N.; Chartier, P.
- International Journal of Electrochemical Science, Vol. 5, Issue 4
Works referencing / citing this record:
Atomistic Investigation of Doping Effects on Electrocatalytic Properties of Cobalt Oxides for Water Oxidation
journal, October 2018
- Kim, Byunghoon; Park, Inchul; Yoon, Gabin
- Advanced Science, Vol. 5, Issue 12
Well-Defined Palladium Nanoparticles Supported on Siliceous Mesocellular Foam as Heterogeneous Catalysts for the Oxidation of Water
journal, March 2015
- Verho, Oscar; Åkermark, Torbjörn; Johnston, Eric V.
- Chemistry - A European Journal, Vol. 21, Issue 15
Laser Fragmentation‐Induced Defect‐Rich Cobalt Oxide Nanoparticles for Electrochemical Oxygen Evolution Reaction
journal, December 2019
- Yu, Mingquan; Waag, Friedrich; Chan, Candace K.
- ChemSusChem, Vol. 13, Issue 3
An Unconventional Iron Nickel Catalyst for the Oxygen Evolution Reaction
journal, February 2019
- Song, Fang; Busch, Michael M.; Lassalle-Kaiser, Benedikt
- ACS Central Science, Vol. 5, Issue 3
Evaluating the Stability of Co 2 P Electrocatalysts in the Hydrogen Evolution Reaction for Both Acidic and Alkaline Electrolytes
journal, May 2018
- Zhang, Yue; Gao, Lu; Hensen, Emiel J. M.
- ACS Energy Letters, Vol. 3, Issue 6
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
Reversible adapting layer produces robust single-crystal electrocatalyst for oxygen evolution
journal, August 2015
- Tung, Ching-Wei; Hsu, Ying-Ya; Shen, Yen-Ping
- Nature Communications, Vol. 6, Issue 1
Coordination tuning of cobalt phosphates towards efficient water oxidation catalyst
journal, September 2015
- Kim, Hyunah; Park, Jimin; Park, Inchul
- Nature Communications, Vol. 6, Issue 1
Screening highly active perovskites for hydrogen-evolving reaction via unifying ionic electronegativity descriptor
journal, August 2019
- Guan, Daqin; Zhou, Jing; Huang, Yu-Cheng
- Nature Communications, Vol. 10, Issue 1
Iron-facilitated dynamic active-site generation on spinel CoAl2O4 with self-termination of surface reconstruction for water oxidation
journal, August 2019
- Wu, Tianze; Sun, Shengnan; Song, Jiajia
- Nature Catalysis, Vol. 2, Issue 9
How covalence breaks adsorption-energy scaling relations and solvation restores them
journal, January 2017
- Calle-Vallejo, Federico; Krabbe, Alexander; García-Lastra, Juan M.
- Chemical Science, Vol. 8, Issue 1
Practical Cluster Models for a Layered β-NiOOH Material
journal, April 2017
- Butera, Valeria; Toroker, Maytal Caspary
- Materials, Vol. 10, Issue 5
Synthesis of Ordered Mesoporous CuO/CeO2 Composite Frameworks as Anode Catalysts for Water Oxidation
journal, November 2015
- Markoulaki Ι, Vassiliki; Papadas, Ioannis; Kornarakis, Ioannis
- Nanomaterials, Vol. 5, Issue 4