Understanding the Oxygen Evolution Reaction Mechanism on CoO x using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy
Abstract
Photoelectrochemical water splitting is a promising approach for renewable production of hydrogen from solar energy and requires interfacing advanced water-splitting catalysts with semiconductors. Understanding the mechanism of function of such electrocatalysts at the atomic scale and under realistic working conditions is a challenging, yet important, task for advancing efficient and stable function. This is particularly true for the case of oxygen evolution catalysts and, here, we study a highly active Co 3O 4/Co(OH) 2 biphasic electrocatalyst on Si by means of operando ambient-pressure X-ray photoelectron spectroscopy performed at the solid/liquid electrified interface. Spectral simulation and multiplet fitting reveal that the catalyst undergoes chemical-structural transformations as a function of the applied anodic potential, with complete conversion of the Co(OH) 2 and partial conversion of the spinel Co 3O 4 phases to CoO(OH) under precatalytic electrochemical conditions. Furthermore, we observe new spectral features in both Co 2p and O 1s core-level regions to emerge under oxygen evolution reaction conditions on CoO(OH). The operando photoelectron spectra support assignment of these newly observed features to highly active Co 4+ centers under catalytic conditions. Comparison of these results to those from a pure phase spinel Co 3O 4 catalyst supports this interpretation and reveals thatmore »
- Authors:
-
[3];
[2];
[2];
[2]
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Helmholtz-Zentrum Berlin fur Materialien und Energie GmbH, Berlin (Germany)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- IOM-CNR, Trieste (Italy)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1379905
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 139; 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; water splitting; cobalt oxide photoelectrocatalysts; operando spectroscopy; ambient pressure XPS; oxygen evolution reaction mechanism
Citation Formats
Favaro, Marco, Yang, Jinhui, Nappini, Silvia, Magnano, Elena, Toma, Francesca M., Crumlin, Ethan J., Yano, Junko, and Sharp, Ian D. Understanding the Oxygen Evolution Reaction Mechanism on CoOx using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy. United States: N. p., 2017.
Web. doi:10.1021/jacs.7b03211.
Favaro, Marco, Yang, Jinhui, Nappini, Silvia, Magnano, Elena, Toma, Francesca M., Crumlin, Ethan J., Yano, Junko, & Sharp, Ian D. Understanding the Oxygen Evolution Reaction Mechanism on CoOx using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy. United States. https://doi.org/10.1021/jacs.7b03211
Favaro, Marco, Yang, Jinhui, Nappini, Silvia, Magnano, Elena, Toma, Francesca M., Crumlin, Ethan J., Yano, Junko, and Sharp, Ian D. Fri .
"Understanding the Oxygen Evolution Reaction Mechanism on CoOx using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy". United States. https://doi.org/10.1021/jacs.7b03211. https://www.osti.gov/servlets/purl/1379905.
@article{osti_1379905,
title = {Understanding the Oxygen Evolution Reaction Mechanism on CoOx using Operando Ambient-Pressure X-ray Photoelectron Spectroscopy},
author = {Favaro, Marco and Yang, Jinhui and Nappini, Silvia and Magnano, Elena and Toma, Francesca M. and Crumlin, Ethan J. and Yano, Junko and Sharp, Ian D.},
abstractNote = {Photoelectrochemical water splitting is a promising approach for renewable production of hydrogen from solar energy and requires interfacing advanced water-splitting catalysts with semiconductors. Understanding the mechanism of function of such electrocatalysts at the atomic scale and under realistic working conditions is a challenging, yet important, task for advancing efficient and stable function. This is particularly true for the case of oxygen evolution catalysts and, here, we study a highly active Co3O4/Co(OH)2 biphasic electrocatalyst on Si by means of operando ambient-pressure X-ray photoelectron spectroscopy performed at the solid/liquid electrified interface. Spectral simulation and multiplet fitting reveal that the catalyst undergoes chemical-structural transformations as a function of the applied anodic potential, with complete conversion of the Co(OH)2 and partial conversion of the spinel Co3O4 phases to CoO(OH) under precatalytic electrochemical conditions. Furthermore, we observe new spectral features in both Co 2p and O 1s core-level regions to emerge under oxygen evolution reaction conditions on CoO(OH). The operando photoelectron spectra support assignment of these newly observed features to highly active Co4+ centers under catalytic conditions. Comparison of these results to those from a pure phase spinel Co3O4 catalyst supports this interpretation and reveals that the presence of Co(OH)2 enhances catalytic activity by promoting transformations to CoO(OH). The direct investigation of electrified interfaces presented in this work can be extended to different materials under realistic catalytic conditions, thereby providing a powerful tool for mechanism discovery and an enabling capability for catalyst design.},
doi = {10.1021/jacs.7b03211},
url = {https://www.osti.gov/biblio/1379905},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 26,
volume = 139,
place = {United States},
year = {2017},
month = {6}
}
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Recent Progress in Bifunctional Electrocatalysts for Overall Water Splitting under Acidic Conditions
journal, May 2019
- Jin, Haneul; Joo, Jinwhan; Chaudhari, Nitin K.
- ChemElectroChem, Vol. 6, Issue 13
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journal, May 2019
- Jin, Haneul; Joo, Jinwhan; Chaudhari, Nitin K.
- ChemElectroChem, Vol. 6, Issue 13
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journal, March 2019
- Gao, Junfeng; Cupolillo, Anna; Nappini, Silvia
- Advanced Functional Materials, Vol. 29, Issue 26
Tracking Structural Self-Reconstruction and Identifying True Active Sites toward Cobalt Oxychloride Precatalyst of Oxygen Evolution Reaction
journal, January 2019
- Jiang, Hongliang; He, Qun; Li, Xiyu
- Advanced Materials, Vol. 31, Issue 8
Amorphous Ni–Fe–Mo Suboxides Coupled with Ni Network as Porous Nanoplate Array on Nickel Foam: A Highly Efficient and Durable Bifunctional Electrode for Overall Water Splitting
journal, February 2020
- Li, Yong‐Ke; Zhang, Geng; Lu, Wang‐Ting
- Advanced Science, Vol. 7, Issue 7
Zn 0.35 Co 0.65 O – A Stable and Highly Active Oxygen Evolution Catalyst Formed by Zinc Leaching and Tetrahedral Coordinated Cobalt in Wurtzite Structure
journal, April 2019
- Wahl, Sebastian; El‐Refaei, Sayed M.; Buzanich, Ana Guilherme
- Advanced Energy Materials, Vol. 9, Issue 20
In-situ-Methoden zur Charakterisierung elektrochemischer NiFe-Sauerstoffentwicklungskatalysatoren
journal, November 2018
- Zhu, Kaiyue; Zhu, Xuefeng; Yang, Weishen
- Angewandte Chemie, Vol. 131, Issue 5
Application of In Situ Techniques for the Characterization of NiFe-Based Oxygen Evolution Reaction (OER) Electrocatalysts
journal, November 2018
- Zhu, Kaiyue; Zhu, Xuefeng; Yang, Weishen
- Angewandte Chemie International Edition, Vol. 58, Issue 5
The Structure of the Cobalt Oxide/Au Catalyst Interface in Electrochemical Water Splitting
journal, August 2018
- Fester, Jakob; Makoveev, Anton; Grumelli, Doris
- Angewandte Chemie International Edition, Vol. 57, Issue 37
Operando X-Ray Absorption Spectroscopy Shows Iron Oxidation Is Concurrent with Oxygen Evolution in Cobalt-Iron (Oxy)hydroxide Electrocatalysts
journal, September 2018
- Enman, Lisa J.; Stevens, Michaela Burke; Dahan, Meir Haim
- Angewandte Chemie International Edition, Vol. 57, Issue 39
Cobalt Incorporated Hydroxyapatite Catalyst for Water Oxidation
journal, October 2019
- Pyo, Eunji; Lee, Keunyoung; Jang, Myeong Je
- ChemCatChem, Vol. 11, Issue 22
Simultaneous Modulation of Composition and Oxygen Vacancies on Hierarchical ZnCo 2 O 4 /Co 3 O 4 /NC‐CNT Mesoporous Dodecahedron for Enhanced Oxygen Evolution Reaction
journal, November 2018
- Ma, Yangde; Yang, Yang; Dai, Xiaoping
- Chemistry – A European Journal, Vol. 24, Issue 70
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
Oxygen reduction reaction mechanism and kinetics on M-NxCy and M@N-C active sites present in model M-N-C catalysts under alkaline and acidic conditions
journal, November 2019
- Sgarbi, Ricardo; Kumar, Kavita; Jaouen, Frédéric
- Journal of Solid State Electrochemistry
Porous Pt nanoframes decorated with Bi(OH)3 as highly efficient and stable electrocatalyst for ethanol oxidation reaction
journal, January 2020
- Yuan, Xiaolei; Jiang, Bei; Cao, Muhan
- Nano Research, Vol. 13, Issue 1
Co3O4 Nanosheet Arrays on Ni Foam as Electrocatalyst for Oxygen Evolution Reaction
journal, May 2018
- Yu, Youyi; Zhang, Jiali; Zhong, Min
- Electrocatalysis, Vol. 9, Issue 6
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
Unified structural motifs of the catalytically active state of Co(oxyhydr)oxides during the electrochemical oxygen evolution reaction
journal, September 2018
- Bergmann, Arno; Jones, Travis E.; Martinez Moreno, Elias
- Nature Catalysis, Vol. 1, Issue 9
The formation of (NiFe)S 2 pyrite mesocrystals as efficient pre-catalysts for water oxidation
journal, January 2018
- Ni, Bing; He, Ting; Wang, Jia-ou
- Chemical Science, Vol. 9, Issue 10
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
Atomically-defined model catalysts in ultrahigh vacuum and in liquid electrolytes: particle size-dependent CO adsorption on Pt nanoparticles on ordered Co 3 O 4 (111) films
journal, January 2018
- Faisal, Firas; Stumm, Corinna; Bertram, Manon
- Physical Chemistry Chemical Physics, Vol. 20, Issue 36
Electrochemical flow cell enabling operando probing of electrocatalyst surfaces by X-ray spectroscopy and diffraction
journal, January 2019
- Farmand, Maryam; Landers, Alan T.; Lin, John C.
- Physical Chemistry Chemical Physics, Vol. 21, Issue 10
Catalysis by design: development of a bifunctional water splitting catalyst through an operando measurement directed optimization cycle
journal, January 2018
- Kornienko, Nikolay; Heidary, Nina; Cibin, Giannantonio
- Chemical Science, Vol. 9, Issue 24
The synergetic effect of h-BN shells and subsurface B in CoB x @h-BN nanocatalysts for enhanced oxygen evolution reactions
journal, January 2018
- Chen, Siru; Li, Yanqiang; Zhang, Zhihua
- Journal of Materials Chemistry A, Vol. 6, Issue 23
A multifunctional vanadium-doped cobalt oxide layer on silicon photoanodes for efficient and stable photoelectrochemical water oxidation
journal, January 2018
- Xing, Zhuo; Wu, Hengyi; Wu, Liang
- Journal of Materials Chemistry A, Vol. 6, Issue 42
Operando diffuse reflectance UV-vis spectroelectrochemistry for investigating oxygen evolution electrocatalysts
journal, January 2020
- Wahl, Sebastian; El-Refaei, Sayed M.; Amsalem, Patrick
- Catalysis Science & Technology, Vol. 10, Issue 2
α(β)-PbO 2 doped with Co 3 O 4 and CNT porous composite materials with enhanced electrocatalytic activity for zinc electrowinning
journal, January 2020
- Wang, Xuanbing; Xu, Ruidong; Feng, Suyang
- RSC Advances, Vol. 10, Issue 3
Improving the oxygen evolution activity of Co 3 O 4 by introducing Ce species derived from Ce-substituted ZIF-67
journal, January 2019
- Zhou, Jieming; Zheng, Haiyan; Luan, Qingjie
- Sustainable Energy & Fuels, Vol. 3, Issue 11
Self-limited growth of an oxyhydroxide phase at the Fe 3 O 4 (001) surface in liquid and ambient pressure water
journal, October 2019
- Kraushofer, Florian; Mirabella, Francesca; Xu, Jian
- The Journal of Chemical Physics, Vol. 151, Issue 15
Interface Science Using Ambient Pressure Hard X-ray Photoelectron Spectroscopy
journal, January 2019
- Favaro, Marco; Abdi, Fatwa; Crumlin, Ethan
- Surfaces, Vol. 2, Issue 1