Short O–O separation in layered oxide Na 0.67 CoO 2 enables an ultrafast oxygen evolution reaction
Abstract
The layered oxide Na0.67CoO2 with Na+ occupying trigonal prismatic sites between CoO2 layers exhibits a remarkably high room temperature oxygen evolution reaction (OER) activity in alkaline solution. The high activity is attributed to an unusually short O-O separation that favors formation of peroxide ions by O--O- interactions followed by O2 evolution in preference to the conventional route through surface O-OH- species. The dependence of the onset potential on the pH of the alkaline solution was found to be consistent with the loss of H+ ions from the surface oxygen to provide surface O- that may either be attacked by solution OH- or react with another O-; a short O-O separation favors the latter route. The role of a strong hybridization of the O-2p and low-spin CoIII/CoIV π-bonding d states is also important; the OER on other CoIII/CoIV oxides is compared with that on Na0.67CoO2 as well as that on IrO2.
- Authors:
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division (SC-22.3)
- OSTI Identifier:
- 1573105
- Alternate Identifier(s):
- OSTI ID: 1597518; OSTI ID: 1601212
- Grant/Contract Number:
- AC02-76SF00515; EE000762; F-1066; AC02-05CH11231; AC02-06CH11357
- Resource Type:
- Published Article
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 116 Journal Issue: 47; Journal ID: ISSN 0027-8424
- Publisher:
- National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; air electrodes; water electrolysis; catalytic mechanisms; structure−property relationship
Citation Formats
Wang, Hao, Wu, Jinpeng, Dolocan, Andrei, Li, Yutao, Lü, Xujie, Wu, Nan, Park, Kyusung, Xin, Sen, Lei, Ming, Yang, Wanli, and Goodenough, John B. Short O–O separation in layered oxide Na 0.67 CoO 2 enables an ultrafast oxygen evolution reaction. United States: N. p., 2019.
Web. doi:10.1073/pnas.1901046116.
Wang, Hao, Wu, Jinpeng, Dolocan, Andrei, Li, Yutao, Lü, Xujie, Wu, Nan, Park, Kyusung, Xin, Sen, Lei, Ming, Yang, Wanli, & Goodenough, John B. Short O–O separation in layered oxide Na 0.67 CoO 2 enables an ultrafast oxygen evolution reaction. United States. https://doi.org/10.1073/pnas.1901046116
Wang, Hao, Wu, Jinpeng, Dolocan, Andrei, Li, Yutao, Lü, Xujie, Wu, Nan, Park, Kyusung, Xin, Sen, Lei, Ming, Yang, Wanli, and Goodenough, John B. Mon .
"Short O–O separation in layered oxide Na 0.67 CoO 2 enables an ultrafast oxygen evolution reaction". United States. https://doi.org/10.1073/pnas.1901046116.
@article{osti_1573105,
title = {Short O–O separation in layered oxide Na 0.67 CoO 2 enables an ultrafast oxygen evolution reaction},
author = {Wang, Hao and Wu, Jinpeng and Dolocan, Andrei and Li, Yutao and Lü, Xujie and Wu, Nan and Park, Kyusung and Xin, Sen and Lei, Ming and Yang, Wanli and Goodenough, John B.},
abstractNote = {The layered oxide Na0.67CoO2 with Na+ occupying trigonal prismatic sites between CoO2 layers exhibits a remarkably high room temperature oxygen evolution reaction (OER) activity in alkaline solution. The high activity is attributed to an unusually short O-O separation that favors formation of peroxide ions by O--O- interactions followed by O2 evolution in preference to the conventional route through surface O-OH- species. The dependence of the onset potential on the pH of the alkaline solution was found to be consistent with the loss of H+ ions from the surface oxygen to provide surface O- that may either be attacked by solution OH- or react with another O-; a short O-O separation favors the latter route. The role of a strong hybridization of the O-2p and low-spin CoIII/CoIV π-bonding d states is also important; the OER on other CoIII/CoIV oxides is compared with that on Na0.67CoO2 as well as that on IrO2.},
doi = {10.1073/pnas.1901046116},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 47,
volume = 116,
place = {United States},
year = {2019},
month = {11}
}
https://doi.org/10.1073/pnas.1901046116
Web of Science
Works referenced in this record:
Branching ratio in x-ray absorption spectroscopy
journal, August 1988
- Thole, B. T.; van der Laan, G.
- Physical Review B, Vol. 38, Issue 5
Synchrotron X-ray Analytical Techniques for Studying Materials Electrochemistry in Rechargeable Batteries
journal, September 2017
- Lin, Feng; Liu, Yijin; Yu, Xiqian
- Chemical Reviews, Vol. 117, Issue 21
Defect Chemistry of Nonprecious-Metal Electrocatalysts for Oxygen Reactions
journal, May 2017
- Yan, Dafeng; Li, Yunxiao; Huo, Jia
- Advanced Materials, Vol. 29, Issue 48
Developing soft X-ray spectroscopy for in situ characterization of nanocatalysts in catalytic reactions
journal, December 2014
- Zhang, Hui; Wang, Wei-Cheng; Glans, Per-Anders
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 197
Covalency-reinforced oxygen evolution reaction catalyst
journal, September 2015
- Yagi, Shunsuke; Yamada, Ikuya; Tsukasaki, Hirofumi
- Nature Communications, Vol. 6, Issue 1
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
Bifunctional Oxygen Reaction Catalysis of Quadruple Manganese Perovskites
journal, November 2016
- Yamada, Ikuya; Fujii, Hiroshi; Takamatsu, Akihiko
- Advanced Materials, Vol. 29, Issue 4
Balancing activity, stability and conductivity of nanoporous core-shell iridium/iridium oxide oxygen evolution catalysts
journal, November 2017
- Kim, Yong-Tae; Lopes, Pietro Papa; Park, Shin-Ae
- Nature Communications, Vol. 8, Issue 1
Transition Metal Oxides as Electrocatalysts for the Oxygen Evolution Reaction in Alkaline Solutions: An Application-Inspired Renaissance
journal, May 2018
- Song, Fang; Bai, Lichen; Moysiadou, Aliki
- Journal of the American Chemical Society, Vol. 140, Issue 25
Multiplet effects in X-ray spectroscopy
journal, January 2005
- Groot, Frank de
- Coordination Chemistry Reviews, Vol. 249, Issue 1-2
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
Spinel-type lithium cobalt oxide as a bifunctional electrocatalyst for the oxygen evolution and oxygen reduction reactions
journal, May 2014
- Maiyalagan, Thandavarayan; Jarvis, Karalee A.; Therese, Soosairaj
- Nature Communications, Vol. 5, Issue 1
Transition-Metal (Co, Ni, and Fe)-Based Electrocatalysts for the Water Oxidation Reaction
journal, August 2016
- Han, Lei; Dong, Shaojun; Wang, Erkang
- Advanced Materials, Vol. 28, Issue 42
Towards identifying the active sites on RuO 2 (110) in catalyzing oxygen evolution
journal, January 2017
- Rao, Reshma R.; Kolb, Manuel J.; Halck, Niels Bendtsen
- Energy & Environmental Science, Vol. 10, Issue 12
The Role of the Lower Metal Oxide/Higher Metal Oxide Couple in Oxygen Evolution Reactions
journal, January 1984
- Rasiyah, P.
- Journal of The Electrochemical Society, Vol. 131, Issue 4
Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions
journal, January 2015
- Jiao, Yan; Zheng, Yao; Jaroniec, Mietek
- Chemical Society Reviews, Vol. 44, Issue 8
Theory-driven design of high-valence metal sites for water oxidation confirmed using in situ soft X-ray absorption
journal, November 2017
- Zheng, Xueli; Zhang, Bo; De Luna, Phil
- Nature Chemistry, Vol. 10, Issue 2
Bulk sensitive x-ray absorption spectroscopy free of self-absorption effects
journal, February 2011
- Achkar, A. J.; Regier, T. Z.; Wadati, H.
- Physical Review B, Vol. 83, Issue 8
Activation of surface oxygen sites on an iridium-based model catalyst for the oxygen evolution reaction
journal, December 2016
- Grimaud, Alexis; Demortière, Arnaud; Saubanère, Matthieu
- Nature Energy, Vol. 2, Issue 1
Modification of Transition-Metal Redox by Interstitial Water in Hexacyanometalate Electrodes for Sodium-Ion Batteries
journal, December 2017
- Wu, Jinpeng; Song, Jie; Dai, Kehua
- Journal of the American Chemical Society, Vol. 139, Issue 50
Electrochemical Catalyst–Support Effects and Their Stabilizing Role for IrO x Nanoparticle Catalysts during the Oxygen Evolution Reaction
journal, September 2016
- Oh, Hyung-Suk; Nong, Hong Nhan; Reier, Tobias
- Journal of the American Chemical Society, Vol. 138, Issue 38
Identification of Surface Reactivity Descriptor for Transition Metal Oxides in Oxygen Evolution Reaction
journal, August 2016
- Tao, Hua Bing; Fang, Liwen; Chen, Jiazang
- Journal of the American Chemical Society, Vol. 138, Issue 31
Impact of Surface Area in Evaluation of Catalyst Activity
journal, June 2018
- Sun, Shengnan; Li, Haiyan; Xu, Zhichuan J.
- Joule, Vol. 2, Issue 6
Determination of total x-ray absorption coefficient using non-resonant x-ray emission
journal, December 2011
- Achkar, A. J.; Regier, T. Z.; Monkman, E. J.
- Scientific Reports, Vol. 1, Issue 1
Revealing the planar chemistry of two-dimensional heterostructures at the atomic level
journal, June 2015
- Chou, Harry; Ismach, Ariel; Ghosh, Rudresh
- Nature Communications, Vol. 6, Issue 1
Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO 3 Perovskites
journal, February 2016
- Petrie, Jonathan R.; Cooper, Valentino R.; Freeland, John W.
- Journal of the American Chemical Society, Vol. 138, Issue 8
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
A Complete High-to-Low spin state Transition of Trivalent Cobalt Ion in Octahedral Symmetry in SrCo 0.5 Ru 0.5 O 3-δ
journal, January 2014
- Chen, Jin-Ming; Chin, Yi-Ying; Valldor, Martin
- Journal of the American Chemical Society, Vol. 136, Issue 4
Nonstoichiometric Oxides as Low-Cost and Highly-Efficient Oxygen Reduction/Evolution Catalysts for Low-Temperature Electrochemical Devices
journal, August 2015
- Chen, Dengjie; Chen, Chi; Baiyee, Zarah Medina
- Chemical Reviews, Vol. 115, Issue 18
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
Distinct Solid-Electrolyte-Interphases on Sn (100) and (001) Electrodes Studied by Soft X-Ray Spectroscopy
journal, February 2014
- Qiao, Ruimin; Lucas, Ivan T.; Karim, Altaf
- Advanced Materials Interfaces, Vol. 1, Issue 3
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
Identifying the Active Surfaces of Electrochemically Tuned LiCoO 2 for Oxygen Evolution Reaction
journal, April 2017
- Lu, Zhiyi; Chen, Guangxu; Li, Yanbin
- Journal of the American Chemical Society, Vol. 139, Issue 17
Investigating the origin of Co(IV)’s high electrocatalytic activity in the oxygen evolution reaction at a Na CoO2 interface
journal, November 2017
- Ji, Huiwen; Sahasrabudhe, Girija; Vallon, Matthew K.
- Materials Research Bulletin, Vol. 95
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
A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles
journal, October 2011
- Suntivich, J.; May, K. J.; Gasteiger, H. A.
- Science, Vol. 334, Issue 6061
Exceptional oxygen evolution reactivities on CaCoO 3 and SrCoO 3
journal, August 2019
- Li, Xiang; Wang, Hao; Cui, Zhiming
- Science Advances, Vol. 5, Issue 8
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
Surface protonation and electrochemical activity of oxides in aqueous solution
journal, March 1990
- Goodenough, John B.; Manoharan, R.; Paranthaman, M.
- Journal of the American Chemical Society, Vol. 112, Issue 6
Quantitative probe of the transition metal redox in battery electrodes through soft x-ray absorption spectroscopy
journal, September 2016
- Li, Qinghao; Qiao, Ruimin; Wray, L. Andrew
- Journal of Physics D: Applied Physics, Vol. 49, Issue 41
Electrochemical tuning of layered lithium transition metal oxides for improvement of oxygen evolution reaction
journal, July 2014
- Lu, Zhiyi; Wang, Haotian; Kong, Desheng
- Nature Communications, Vol. 5, Issue 1
Influence of Surface Adsorption on the Oxygen Evolution Reaction on IrO 2 (110)
journal, February 2017
- Kuo, Ding-Yuan; Kawasaki, Jason K.; Nelson, Jocienne N.
- Journal of the American Chemical Society, Vol. 139, Issue 9
Key electronic states in lithium battery materials probed by soft X-ray spectroscopy
journal, October 2013
- Yang, Wanli; Liu, Xiaosong; Qiao, Ruimin
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 190