X-ray spectroscopic characterization of Co(IV) and metal–metal interactions in Co4O4: Electronic structure contributions to the formation of high-valent states relevant to the oxygen evolution reaction

Hadt, Ryan G.; Hayes, Dugan; Brodsky, Casey N.; Ullman, Andrew M.; Casa, Diego M.; Upton, Mary H.; Nocera, Daniel G.; Chen, Lin X.

doi:10.1021/jacs.6b04663

Title: X-ray spectroscopic characterization of Co(IV) and metal–metal interactions in Co₄O₄: Electronic structure contributions to the formation of high-valent states relevant to the oxygen evolution reaction

Journal Article · Fri Aug 12 00:00:00 EDT 2016 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.6b04663· OSTI ID:1339577

Hadt, Ryan G. ^[1]; Hayes, Dugan ^[1]; Brodsky, Casey N. ^[2]; Ullman, Andrew M. ^[2]; Casa, Diego M. ^[1]; Upton, Mary H. ^[1]; Nocera, Daniel G. ^[2]; Chen, Lin X. ^[3]

Argonne National Lab. (ANL), Lemont, IL (United States)
Harvard Univ., Cambridge, MA (United States)
Argonne National Lab. (ANL), Lemont, IL (United States); Northwestern Univ., Evanston, IL (United States)

In this paper, the formation of high-valent states is a key factor in making highly active transition metal-based catalysts of the oxygen-evolving reaction (OER). These high oxidation states will be strongly influenced by the local geometric and electronic structures of the metal ion, which is difficult to study due to spectroscopically active and complex backgrounds, short lifetimes, and limited concentrations. Here, we use a wide range of complementary X-ray spectroscopies coupled to DFT calculations to study Co₄O₄ cubanes, which provide insight into the high-valent Co(IV) centers responsible for the activity of molecular and heterogeneous OER catalysts. The combination of X-ray absorption and 1s3p resonant inelastic X-ray scattering (Kβ RIXS) allow Co(IV) to be isolated and studied against a spectroscopically active Co(III) background. Co K- and L-edge X-ray absorption data allow for a detailed characterization of the 3d-manifold of effectively localized Co(IV) centers and provide a direct handle on the ligand field environment and covalency of the t_2g-based redox active molecular orbital. Kβ RIXS is also shown to provide a powerful probe of Co(IV), and specific spectral features are sensitive to the degree of oxo-mediated metal-metal coupling across Co₄O₄. Guided by the data, calculations show electron-hole delocalization can actually oppose Co(IV) formation. Computational extension of Co₄O₄ to CoM₃O₄ structures (M = redox-inactive metal) defines electronic structure contri-butions to Co(IV) formation. Redox activity is shown to be linearly related to covalency, and M(III) oxo inductive effects on Co(IV) oxo bonding can tune the covalency of high-valent sites over a large range and thereby tune E⁰ over hundreds of mVs.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1339577

Journal Information:: Journal of the American Chemical Society, Vol. 138, Issue 34; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 80 works

Citation information provided by
Web of Science

References (108)

Powering the planet: Chemical challenges in solar energy utilization Lewis, N. S.; Nocera, D. G. Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735 https://doi.org/10.1073/pnas.0603395103	journal	October 2006
Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds Cook, Timothy R.; Dogutan, Dilek K.; Reece, Steven Y. Chemical Reviews, Vol. 110, Issue 11 https://doi.org/10.1021/cr100246c	journal	November 2010
The Artificial Leaf Nocera, Daniel G. Accounts of Chemical Research, Vol. 45, Issue 5 https://doi.org/10.1021/ar2003013	journal	January 2012
In Situ Formation of an Oxygen-Evolving Catalyst in Neutral Water Containing Phosphate and Co²⁺ Kanan, M. W.; Nocera, D. G. Science, Vol. 321, Issue 5892, p. 1072-1075 https://doi.org/10.1126/science.1162018	journal	August 2008
A Self-Healing Oxygen-Evolving Catalyst Lutterman, Daniel A.; Surendranath, Yogesh; Nocera, Daniel G. Journal of the American Chemical Society, Vol. 131, Issue 11 https://doi.org/10.1021/ja900023k	journal	March 2009
Structure and Valency of a Cobalt−Phosphate Water Oxidation Catalyst Determined by in Situ X-ray Spectroscopy Kanan, Matthew W.; Yano, Junko; Surendranath, Yogesh Journal of the American Chemical Society, Vol. 132, Issue 39 https://doi.org/10.1021/ja1023767	journal	October 2010
Nickel-borate oxygen-evolving catalyst that functions under benign conditions Dinca, M.; Surendranath, Y.; Nocera, D. G. Proceedings of the National Academy of Sciences, Vol. 107, Issue 23 https://doi.org/10.1073/pnas.1001859107	journal	May 2010
Nickel–Iron Oxyhydroxide Oxygen-Evolution Electrocatalysts: The Role of Intentional and Incidental Iron Incorporation Trotochaud, Lena; Young, Samantha L.; Ranney, James K. Journal of the American Chemical Society, Vol. 136, Issue 18 https://doi.org/10.1021/ja502379c	journal	April 2014
Highly Active Mixed-Metal Nanosheet Water Oxidation Catalysts Made by Pulsed-Laser Ablation in Liquids Hunter, Bryan M.; Blakemore, James D.; Deimund, Mark Journal of the American Chemical Society, Vol. 136, Issue 38 https://doi.org/10.1021/ja506087h	journal	September 2014
Water Oxidation Catalysis: Electrocatalytic Response to Metal Stoichiometry in Amorphous Metal Oxide Films Containing Iron, Cobalt, and Nickel Smith, Rodney D. L.; Prévot, Mathieu S.; Fagan, Randal D. Journal of the American Chemical Society, Vol. 135, Issue 31 https://doi.org/10.1021/ja403102j	journal	July 2013
Ultrathin Cobalt–Manganese Layered Double Hydroxide Is an Efficient Oxygen Evolution Catalyst Song, Fang; Hu, Xile Journal of the American Chemical Society, Vol. 136, Issue 47 https://doi.org/10.1021/ja5096733	journal	November 2014
Electrocatalytic Oxygen Evolution over Supported Small Amorphous Ni–Fe Nanoparticles in Alkaline Electrolyte Qiu, Yang; Xin, Le; Li, Wenzhen Langmuir, Vol. 30, Issue 26 https://doi.org/10.1021/la501246e	journal	June 2014
Identification of Highly Active Fe Sites in (Ni,Fe)OOH for Electrocatalytic Water Splitting Friebel, Daniel; Louie, Mary W.; Bajdich, Michal Journal of the American Chemical Society, Vol. 137, Issue 3 https://doi.org/10.1021/ja511559d	journal	January 2015
Metal–Ligand Covalency of Iron Complexes from High-Resolution Resonant Inelastic X-ray Scattering Lundberg, Marcus; Kroll, Thomas; DeBeer, Serena Journal of the American Chemical Society, Vol. 135, Issue 45 https://doi.org/10.1021/ja408072q	journal	October 2013
Resonant Inelastic X-ray Scattering on Ferrous and Ferric Bis-imidazole Porphyrin and Cytochrome c : Nature and Role of the Axial Methionine–Fe Bond Kroll, Thomas; Hadt, Ryan G.; Wilson, Samuel A. Journal of the American Chemical Society, Vol. 136, Issue 52 https://doi.org/10.1021/ja5100367	journal	December 2014
Resonant inelastic x-ray scattering studies of elementary excitations Ament, Luuk J. P.; van Veenendaal, Michel; Devereaux, Thomas P. Reviews of Modern Physics, Vol. 83, Issue 2 https://doi.org/10.1103/RevModPhys.83.705	journal	June 2011
Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper Li, Christina W.; Ciston, Jim; Kanan, Matthew W. Nature, Vol. 508, Issue 7497 https://doi.org/10.1038/nature13249	journal	April 2014
Grain-Boundary-Dependent CO ₂ Electroreduction Activity Feng, Xiaofeng; Jiang, Kaili; Fan, Shoushan Journal of the American Chemical Society, Vol. 137, Issue 14 https://doi.org/10.1021/ja5130513	journal	April 2015
Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts Verdaguer-Casadevall, Arnau; Li, Christina W.; Johansson, Tobias P. Journal of the American Chemical Society, Vol. 137, Issue 31 https://doi.org/10.1021/jacs.5b06227	journal	July 2015
Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO ₃ Perovskites Petrie, Jonathan R.; Cooper, Valentino R.; Freeland, John W. Journal of the American Chemical Society, Vol. 138, Issue 8 https://doi.org/10.1021/jacs.5b11713	journal	February 2016
A [Cu ₂ O] ²⁺ core in Cu-ZSM-5, the active site in the oxidation of methane to methanol Woertink, Julia S.; Smeets, Pieter J.; Groothaert, Marijke H. Proceedings of the National Academy of Sciences, Vol. 106, Issue 45 https://doi.org/10.1073/pnas.0910461106	journal	October 2009
Cu-ZSM-5: A biomimetic inorganic model for methane oxidation Vanelderen, Pieter; Hadt, Ryan G.; Smeets, Pieter J. Journal of Catalysis, Vol. 284, Issue 2 https://doi.org/10.1016/j.jcat.2011.10.009	journal	December 2011
Spectroscopic Definition of the Copper Active Sites in Mordenite: Selective Methane Oxidation Vanelderen, Pieter; Snyder, Benjamin E. R.; Tsai, Ming-Li Journal of the American Chemical Society, Vol. 137, Issue 19 https://doi.org/10.1021/jacs.5b02817	journal	May 2015
The role of proton coupled electron transfer in water oxidation Gagliardi, Christopher J.; Vannucci, Aaron K.; Concepcion, Javier J. Energy & Environmental Science, Vol. 5, Issue 7 https://doi.org/10.1039/c2ee03311a	journal	January 2012
Probing Edge Site Reactivity of Oxidic Cobalt Water Oxidation Catalysts Ullman, Andrew M.; Brodsky, Casey N.; Li, Nancy Journal of the American Chemical Society, Vol. 138, Issue 12 https://doi.org/10.1021/jacs.6b00762	journal	March 2016
Architecture of the Photosynthetic Oxygen-Evolving Center Ferreira, K. N. Science, Vol. 303, Issue 5665 https://doi.org/10.1126/science.1093087	journal	March 2004
Crystal structure of oxygen-evolving photosystem II at a resolution of 1.9 Å Umena, Yasufumi; Kawakami, Keisuke; Shen, Jian-Ren Nature, Vol. 473, Issue 7345 https://doi.org/10.1038/nature09913	journal	April 2011
A synthetic Mn4Ca-cluster mimicking the oxygen-evolving center of photosynthesis Zhang, C.; Chen, C.; Dong, H. Science, Vol. 348, Issue 6235 https://doi.org/10.1126/science.aaa6550	journal	May 2015
Catalytic Oxygen Evolution by Cobalt Oxido Thin Films Bediako, D. Kwabena; Ullman, Andrew M.; Nocera, Daniel G. Topics in Current Chemistry https://doi.org/10.1007/128_2015_649	book	January 2015
Cobalt–phosphate oxygen-evolving compound Kanan, Matthew W.; Surendranath, Yogesh; Nocera, Daniel G. Chemical Society Reviews, Vol. 38, Issue 1, p. 109-114 https://doi.org/10.1039/B802885K	journal	January 2009
The chemistry of cobalt acetate—IV. The isolation and crystal structure of the symmetric cubane, tetrakis[(μ-acetato)(μ3-oxo) (pyridine)cobalt(III)] · chloroform solvate, [Co4(μ3-O)4(μ-CH3CO2)4(C5H5N)in4] · 5CHCl3 and of the dicationic partial cubane, trimeric, [(μ-acetato)(acetato)tris(μ-hdyroxy(μ3-oxo) hexakispyridinetricobalt(III)]hexafluorophosphate · water solvate, [Co3(μ3-O)(μ-OH)3(μ-CH3CO2(CH3CO2(C5H5N)6[PF6]2 · 2H2O Beattie, James K.; Hambley, Trevor W.; Klepetko, John A. Polyhedron, Vol. 17, Issue 8 https://doi.org/10.1016/S0277-5387(97)00300-8	journal	January 1998
Dimerization of the [Co2III(OH)2] core to the first example of a [Co4IIIO4] cubane: potential insights into photosynthetic water oxidation Dimitrou, Katerina; Folting, Kirsten; Streib, William E. Journal of the American Chemical Society, Vol. 115, Issue 14 https://doi.org/10.1021/ja00067a077	journal	July 1993
The [Co4O4]4+ Cubane as a Quadruply-Bridging Unit: The Mixed-Valence Cluster [Co8O4(O2CPh)12(solv)4] (solv = DMF, MeCN, H2O) Dimitrou, Katerina; Sun, Jui-Sui; Folting, Kirsten Inorganic Chemistry, Vol. 34, Issue 16 https://doi.org/10.1021/ic00120a021	journal	August 1995
Mixed-valence, tetranuclear cobalt(iii,iv) complexes: preparation and properties of [Co4O4(O2CR)2(bpy)4]3+ salts Dimitrou, Katerina; Brown, Angelica D.; Christou, George Chemical Communications, Issue 14 https://doi.org/10.1039/b102008k	journal	January 2001
Synthesis, Structure, Spectral and Electrochemical Properties, and Catalytic Use of Cobalt(III)−Oxo Cubane Clusters Chakrabarty, Rajesh; Bora, Sanchay J.; Das, Birinchi K. Inorganic Chemistry, Vol. 46, Issue 22 https://doi.org/10.1021/ic7011759	journal	October 2007
Selective oxidation of alcohols catalysed by a cubane-like Co(III) oxo cluster immobilised on porous organomodified silica Sarmah, Purabi; Chakrabarty, Rajesh; Phukan, Prodeep Journal of Molecular Catalysis A: Chemical, Vol. 268, Issue 1-2 https://doi.org/10.1016/j.molcata.2006.11.042	journal	May 2007
Catalytic Properties of Cobalt(III)−Oxo Cubanes in the TBHP Oxidation of Benzylic Alcohols Chakrabarty, Rajesh; Sarmah, Purabi; Saha, Bapan Inorganic Chemistry, Vol. 48, Issue 14 https://doi.org/10.1021/ic802115n	journal	July 2009
Cobalt(III)-oxo cubane clusters as catalysts for oxidation of organic substrates Das, Birinchi Kumar; Chakrabarty, Rajesh Journal of Chemical Sciences, Vol. 123, Issue 2 https://doi.org/10.1007/s12039-011-0111-6	journal	March 2011
Water Oxidation by the [Co ₄ O ₄ (OAc) ₄ (py) ₄ ] ⁺ Cubium is Initiated by OH ^– Addition Smith, Paul F.; Hunt, Liam; Laursen, Anders B. Journal of the American Chemical Society, Vol. 137, Issue 49 https://doi.org/10.1021/jacs.5b09152	journal	December 2015
A Co ₄ O ₄ “Cubane” Water Oxidation Catalyst Inspired by Photosynthesis McCool, Nicholas S.; Robinson, David M.; Sheats, John E. Journal of the American Chemical Society, Vol. 133, Issue 30 https://doi.org/10.1021/ja203877y	journal	August 2011
Light-driven wateroxidation with a molecular tetra-cobalt(iii) cubanecluster La Ganga, Giuseppina; Puntoriero, Fausto; Campagna, Sebastiano Faraday Discuss., Vol. 155 https://doi.org/10.1039/C1FD00093D	journal	January 2012
Photocatalytic Water Oxidation: Tuning Light-Induced Electron Transfer by Molecular Co ₄ O ₄ Cores Berardi, Serena; La Ganga, Giuseppina; Natali, Mirco Journal of the American Chemical Society, Vol. 134, Issue 27 https://doi.org/10.1021/ja303951z	journal	June 2012
Water Oxidation Mechanism for Synthetic Co–Oxides with Small Nuclearity Li, Xichen; Siegbahn, Per E. M. Journal of the American Chemical Society, Vol. 135, Issue 37 https://doi.org/10.1021/ja4053448	journal	September 2013
Reaction Pathways for Oxygen Evolution Promoted by Cobalt Catalyst Mattioli, Giuseppe; Giannozzi, Paolo; Amore Bonapasta, Aldo Journal of the American Chemical Society, Vol. 135, Issue 41 https://doi.org/10.1021/ja401797v	journal	October 2013
Mechanistic Investigations of Water Oxidation by a Molecular Cobalt Oxide Analogue: Evidence for a Highly Oxidized Intermediate and Exclusive Terminal Oxo Participation Nguyen, Andy I.; Ziegler, Micah S.; Oña-Burgos, Pascual Journal of the American Chemical Society, Vol. 137, Issue 40 https://doi.org/10.1021/jacs.5b08396	journal	September 2015
Water Oxidation Catalysis by Co(II) Impurities in Co(III) ₄ O ₄ Cubanes Ullman, Andrew M.; Liu, Yi; Huynh, Michael Journal of the American Chemical Society, Vol. 136, Issue 50 https://doi.org/10.1021/ja5110393	journal	December 2014
Photo-active Cobalt Cubane Model of an Oxygen-Evolving Catalyst Symes, Mark D.; Lutterman, Daniel A.; Teets, Thomas S. ChemSusChem, Vol. 6, Issue 1 https://doi.org/10.1002/cssc.201200682	journal	January 2013
Bidirectional and Unidirectional PCET in a Molecular Model of a Cobalt-Based Oxygen-Evolving Catalyst Symes, Mark D.; Surendranath, Yogesh; Lutterman, Daniel A. Journal of the American Chemical Society, Vol. 133, Issue 14 https://doi.org/10.1021/ja110908v	journal	April 2011
EPR Evidence for Co(IV) Species Produced During Water Oxidation at Neutral pH McAlpin, J. Gregory; Surendranath, Yogesh; Dincǎ, Mircea Journal of the American Chemical Society, Vol. 132, Issue 20 https://doi.org/10.1021/ja1013344	journal	May 2010
Electronic Structure Description of a [Co(III) ₃ Co(IV)O ₄ ] Cluster: A Model for the Paramagnetic Intermediate in Cobalt-Catalyzed Water Oxidation McAlpin, J. Gregory; Stich, Troy A.; Ohlin, C. André Journal of the American Chemical Society, Vol. 133, Issue 39 https://doi.org/10.1021/ja202320q	journal	October 2011
Structural insights into [Co4O4(C5H5N)4(CH3CO2)4]+, a rare Co(IV)-containing cuboidal complex Stich, Troy A.; Krzystek, J.; Mercado, Brandon Q. Polyhedron, Vol. 64 https://doi.org/10.1016/j.poly.2013.05.038	journal	November 2013
Mixed Valence Chemistry-A Survey and Classification Robin, Melvin B.; Day, Peter Advances in Inorganic Chemistry and Radiochemistry https://doi.org/10.1016/S0065-2792(08)60179-X	book	January 1968
Inequivalent XPS binding energies in symmetrical delocalized mixed-valence complexes Hush, N. S. Chemical Physics, Vol. 10, Issue 2-3 https://doi.org/10.1016/0301-0104(75)87049-2	journal	September 1975
What Determines Catalyst Functionality in Molecular Water Oxidation? Dependence on Ligands and Metal Nuclearity in Cobalt Clusters Smith, Paul F.; Kaplan, Christopher; Sheats, John E. Inorganic Chemistry, Vol. 53, Issue 4 https://doi.org/10.1021/ic402720p	journal	December 2013
Mechanistic Studies of the Oxygen Evolution Reaction by a Cobalt-Phosphate Catalyst at Neutral pH Surendranath, Yogesh; Kanan, Matthew W.; Nocera, Daniel G. Journal of the American Chemical Society, Vol. 132, Issue 46 https://doi.org/10.1021/ja106102b	journal	November 2010
Proton–Electron Transport and Transfer in Electrocatalytic Films. Application to a Cobalt-Based O ₂ -Evolution Catalyst Bediako, D. Kwabena; Costentin, Cyrille; Jones, Evan C. Journal of the American Chemical Society, Vol. 135, Issue 28 https://doi.org/10.1021/ja403656w	journal	May 2013
Mechanism of Cobalt Self-Exchange Electron Transfer Ullman, Andrew M.; Nocera, Daniel G. Journal of the American Chemical Society, Vol. 135, Issue 40 https://doi.org/10.1021/ja404469y	journal	September 2013
Conduction and Reactivity in Heterogeneous-Molecular Catalysis: New Insights in Water Oxidation Catalysis by Phosphate Cobalt Oxide Films Costentin, Cyrille; Porter, Thomas R.; Savéant, Jean-Michel Journal of the American Chemical Society, Vol. 138, Issue 17 https://doi.org/10.1021/jacs.6b00737	journal	April 2016
Mixed valence: origins and developments Day, Peter; Hush, Noel S.; Clark, Robin J. H. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 366, Issue 1862 https://doi.org/10.1098/rsta.2007.2135	journal	September 2007
Electron transfer at the class II/III borderline of mixed valency: dependence of rates on solvent dynamics and observation of a localized-to-delocalized transition in freezing solvents Glover, Starla D.; Lear, Benjamin J.; Salsman, J. Catherine Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 366, Issue 1862 https://doi.org/10.1098/rsta.2007.2149	journal	September 2007
Mixed Valency at the Nearly Delocalized Limit: Fundamentals and Forecast Glover, Starla D.; Goeltz, John C.; Lear, Benjamin J. European Journal of Inorganic Chemistry, Vol. 2009, Issue 5 https://doi.org/10.1002/ejic.200800910	journal	January 2009
Inter- or intramolecular electron transfer between triruthenium clusters: we’ll cross that bridge when we come to it Glover, Starla D.; Goeltz, John C.; Lear, Benjamin J. Coordination Chemistry Reviews, Vol. 254, Issue 3-4 https://doi.org/10.1016/j.ccr.2009.09.005	journal	February 2010
Optical transitions of symmetrical mixed-valence systems in the Class II–III transition regimeElectronic supplementary information (ESI) is available: derivation of eqn. (39c), table summarizing the relationships between band maxima and band widths predicted by the two-state model and table of spectral properties of mixed-valence ruthenium(II)/(III) bridged by pyrazine and dicyanamide. See http://www.rsc.org/suppdata/cs/b0/b008034i/ Brunschwig, Bruce S.; Creutz, Carol; Sutin, Norman Chemical Society Reviews, Vol. 31, Issue 3 https://doi.org/10.1039/b008034i	journal	April 2002
Charge transfer, hybridization and local inhomogeneity effects in ${Na}_{x} Co O_{2} ∙ y H_{2} O$ : An x-ray absorption spectroscopy study Poltavets, Viktor V.; Croft, Mark; Greenblatt, Martha Physical Review B, Vol. 74, Issue 12 https://doi.org/10.1103/PhysRevB.74.125103	journal	September 2006
A Multiplet Analysis of Fe K-Edge 1s → 3d Pre-Edge Features of Iron Complexes Westre, Tami E.; Kennepohl, Pierre; DeWitt, Jane G. Journal of the American Chemical Society, Vol. 119, Issue 27 https://doi.org/10.1021/ja964352a	journal	July 1997
Studies on the Valence State of Iron Atoms in the Mixed-Valence Binuclear Ferrocenes by X-Ray Absorption Near Edge Structure (XANES) and by X-Ray Photoelectron Spectroscopy (XPS) Iwai, Kumiko; Iwai, Makoto; Suto, Kyoko Bulletin of the Chemical Society of Japan, Vol. 59, Issue 9 https://doi.org/10.1246/bcsj.59.2675	journal	September 1986
Orbital hybridization and spin polarization in the resonant $1 s$ photoexcitations of $α − {Fe}_{2} O_{3}$ Glatzel, Pieter; Mirone, Alessandro; Eeckhout, Sigrid G. Physical Review B, Vol. 77, Issue 11 https://doi.org/10.1103/PhysRevB.77.115133	journal	March 2008
The 1s x-ray absorption pre-edge structures in transition metal oxides de Groot, Frank; Vankó, György; Glatzel, Pieter Journal of Physics: Condensed Matter, Vol. 21, Issue 10 https://doi.org/10.1088/0953-8984/21/10/104207	journal	February 2009
Water oxidation by amorphous cobalt-based oxides: in situ tracking of redox transitions and mode of catalysis Risch, Marcel; Ringleb, Franziska; Kohlhoff, Mike Energy & Environmental Science, Vol. 8, Issue 2 https://doi.org/10.1039/C4EE03004D	journal	January 2015
L-edge X-ray Absorption Spectroscopy of Non-Heme Iron Sites: Experimental Determination of Differential Orbital Covalency Wasinger, Erik C.; de Groot, Frank M. F.; Hedman, Britt Journal of the American Chemical Society, Vol. 125, Issue 42 https://doi.org/10.1021/ja034634s	journal	October 2003
Fe L-Edge X-ray Absorption Spectroscopy Determination of Differential Orbital Covalency of Siderophore Model Compounds: Electronic Structure Contributions to High Stability Constants Hocking, Rosalie K.; DeBeer George, Serena; Raymond, Kenneth N. Journal of the American Chemical Society, Vol. 132, Issue 11 https://doi.org/10.1021/ja9090098	journal	March 2010
Spin transition evidenced by soft x-ray absorption spectroscopy Cartier dit Moulin, Christophe; Rudolf, Petra; Flank, Anne Marie The Journal of Physical Chemistry, Vol. 96, Issue 15 https://doi.org/10.1021/j100194a021	journal	July 1992
High resolution 1s core hole X-ray spectroscopy in 3d transition metal complexes—electronic and structural information Glatzel, Pieter; Bergmann, Uwe Coordination Chemistry Reviews, Vol. 249, Issue 1-2 https://doi.org/10.1016/j.ccr.2004.04.011	journal	January 2005
MERIX—Next generation medium energy resolution inelastic X-ray scattering instrument at the APS Shvyd’ko, Yu. V.; Hill, J. P.; Burns, C. A. Journal of Electron Spectroscopy and Related Phenomena, Vol. 188 https://doi.org/10.1016/j.elspec.2012.09.003	journal	June 2013
Direct-Coupling O ₂ Bond Forming a Pathway in Cobalt Oxide Water Oxidation Catalysts Wang, Lee-Ping; Van Voorhis, Troy The Journal of Physical Chemistry Letters, Vol. 2, Issue 17 https://doi.org/10.1021/jz201021n	journal	August 2011
What Can Density Functional Theory Tell Us about Artificial Catalytic Water Splitting? Mavros, Michael G.; Tsuchimochi, Takashi; Kowalczyk, Tim Inorganic Chemistry, Vol. 53, Issue 13 https://doi.org/10.1021/ic5002557	journal	April 2014
Exploring the Ground and Excited State Potential Energy Landscapes of the Mixed-Valence Biferrocenium Complex Hadt, Ryan G.; Nemykin, Victor N. Inorganic Chemistry, Vol. 48, Issue 9 https://doi.org/10.1021/ic801801m	journal	April 2009
Quantifying the effects of the self-interaction error in DFT: When do the delocalized states appear? Lundberg, Marcus; Siegbahn, Per E. M. The Journal of Chemical Physics, Vol. 122, Issue 22 https://doi.org/10.1063/1.1926277	journal	June 2005
Prediction of molecular properties and molecular spectroscopy with density functional theory: From fundamental theory to exchange-coupling Neese, Frank Coordination Chemistry Reviews, Vol. 253, Issue 5-6 https://doi.org/10.1016/j.ccr.2008.05.014	journal	March 2009
Sulfur K-Edge X-ray Absorption Spectroscopy of 2Fe−2S Ferredoxin: Covalency of the Oxidized and Reduced 2Fe Forms and Comparison to Model Complexes Anxolabéhère-Mallart, Elodie; Glaser, Thorsten; Frank, Patrick Journal of the American Chemical Society, Vol. 123, Issue 23 https://doi.org/10.1021/ja010472t	journal	June 2001
Protein Effects on the Electronic Structure of the [Fe ₄ S ₄ ] ²⁺ Cluster in Ferredoxin and HiPIP Glaser, Thorsten; Bertini, Ivano; Moura, Jose J. G. Journal of the American Chemical Society, Vol. 123, Issue 20 https://doi.org/10.1021/ja0155940	journal	May 2001
Solvent Tuning of Electrochemical Potentials in the Active Sites of HiPIP Versus Ferredoxin Dey, A.; Jenney, F. E.; Adams, M. W. W. Science, Vol. 318, Issue 5855 https://doi.org/10.1126/science.1147753	journal	November 2007
Spectroscopic and DFT Studies of Second-Sphere Variants of the Type 1 Copper Site in Azurin: Covalent and Nonlocal Electrostatic Contributions to Reduction Potentials Hadt, Ryan G.; Sun, Ning; Marshall, Nicholas M. Journal of the American Chemical Society, Vol. 134, Issue 40 https://doi.org/10.1021/ja306438n	journal	October 2012
The role of the inductive effect in solid state chemistry: how the chemist can use it to modify both the structural and the physical properties of the materials Etourneau, J.; Portier, J.; Ménil, F. Journal of Alloys and Compounds, Vol. 188 https://doi.org/10.1016/0925-8388(92)90635-M	journal	October 1992
On the Absorption Spectra of Complex Ions. I Tanabe, Yukito; Sugano, Satoru Journal of the Physical Society of Japan, Vol. 9, Issue 5 https://doi.org/10.1143/JPSJ.9.753	journal	September 1954
Stabilization of tetravalent cobalt in an isolated six-coordinated site of an oxide lattice: A magnetic and ESR characterization Buffat, B.; Demazeau, G.; Pouchard, M. Journal of Solid State Chemistry, Vol. 50, Issue 1 https://doi.org/10.1016/0022-4596(83)90230-X	journal	November 1983
Fe L-Edge XAS Studies of K ₄ [Fe(CN) ₆ ] and K ₃ [Fe(CN) ₆ ]: A Direct Probe of Back-Bonding Hocking, Rosalie K.; Wasinger, Erik C.; de Groot, Frank M. F. Journal of the American Chemical Society, Vol. 128, Issue 32 https://doi.org/10.1021/ja061802i	journal	August 2006
Controlled-valence properties of ${La}_{1 - x}$ ${Sr}_{x}$ ${FeO}_{3}$ and ${La}_{1 - x}$ ${Sr}_{x}$ ${MnO}_{3}$ studied by soft-x-ray absorption spectroscopy Abbate, M.; de Groot, F. M. F.; Fuggle, J. C. Physical Review B, Vol. 46, Issue 8 https://doi.org/10.1103/PhysRevB.46.4511	journal	August 1992
The Ordered K2NiF4-type Structure of Mixed Crystals La2−xSrxLi1/2Co1/2O4 (x<0.5) and the Electronic Properties of the Constituting CoIII and CoIV Ions Warda, Salam A.; Massa, Werner; Reinen, Dirk Journal of Solid State Chemistry, Vol. 146, Issue 1 https://doi.org/10.1006/jssc.1999.8311	journal	August 1999
Multiplet effects in X-ray spectroscopy Groot, Frank de Coordination Chemistry Reviews, Vol. 249, Issue 1-2 https://doi.org/10.1016/j.ccr.2004.03.018	journal	January 2005
Differences between L ₃ and L ₂ x‐ray absorption spectra of transition metal compounds de Groot, F. M. F.; Hu, Z. W.; Lopez, M. F. The Journal of Chemical Physics, Vol. 101, Issue 8 https://doi.org/10.1063/1.468351	journal	October 1994
On the magnetic properties of covalentXY₆complexes Stevens, K. W. H.; Pryce, Maurice Henry Lecorney Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, Vol. 219, Issue 1139, p. 542-555 https://doi.org/10.1098/rspa.1953.0166	journal	October 1953
The magnetic properties of transition metal ions in asymmetric ligand fields. Part 2.—Cubic field ₃ T ₂ terms. Figgis, B. N. Trans. Faraday Soc., Vol. 57, Issue 0 https://doi.org/10.1039/TF9615700198	journal	January 1961
The EPR of low spin heme complexes Relation of the τ2g hole model to the directional properties of the g tensor, and a new method for calculating the ligand field parameters Taylor, C. P. S. Biochimica et Biophysica Acta (BBA) - Protein Structure, Vol. 491, Issue 1 https://doi.org/10.1016/0005-2795(77)90049-6	journal	March 1977
Oxygen Evolution Reaction on La _{1– x} Sr _x CoO ₃ Perovskites: A Combined Experimental and Theoretical Study of Their Structural, Electronic, and Electrochemical Properties Cheng, Xi; Fabbri, Emiliana; Nachtegaal, Maarten Chemistry of Materials, Vol. 27, Issue 22 https://doi.org/10.1021/acs.chemmater.5b03138	journal	November 2015
X-Ray Co K Edges of [Co(CN) ₆ ] ^3- , [Co(NO ₂ ) ₆ ] ^3- and [Co(NCS) ₄ ] ^2- Complex Ions Obashi, Masayoshi Japanese Journal of Applied Physics, Vol. 16, Issue 1 https://doi.org/10.1143/JJAP.16.167	journal	January 1977
Angular dependence of core hole screening in ${LiCoO}_{2}$ : A $DFT + U$ calculation of the oxygen and cobalt $K$ -edge x-ray absorption spectra Juhin, Amélie; de Groot, Frank; Vankó, György Physical Review B, Vol. 81, Issue 11 https://doi.org/10.1103/PhysRevB.81.115115	journal	March 2010
Direct approach to measuring the Franck-Condon barrier to electron transfer between metal ions Creutz, Carol; Taube, Henry Journal of the American Chemical Society, Vol. 91, Issue 14 https://doi.org/10.1021/ja01042a072	journal	July 1969
Redox-inactive metals modulate the reduction potential in heterometallic manganese–oxido clusters Tsui, Emily Y.; Tran, Rosalie; Yano, Junko Nature Chemistry, Vol. 5, Issue 4 https://doi.org/10.1038/nchem.1578	journal	March 2013
Investigations of the Effect of the Non-Manganese Metal in Heterometallic-Oxido Cluster Models of the Oxygen Evolving Complex of Photosystem II: Lanthanides as Substitutes for Calcium Lin, Po-Heng; Takase, Michael K.; Agapie, Theodor Inorganic Chemistry, Vol. 54, Issue 1 https://doi.org/10.1021/ic5015219	journal	December 2014
Redox potential tuning by redox-inactive cations in nature's water oxidizing catalyst and synthetic analogues Krewald, Vera; Neese, Frank; Pantazis, Dimitrios A. Physical Chemistry Chemical Physics, Vol. 18, Issue 16 https://doi.org/10.1039/C5CP07213A	journal	January 2016
3d–4f {Co ^II ₃ Ln(OR) ₄ } Cubanes as Bio-Inspired Water Oxidation Catalysts Evangelisti, Fabio; Moré, René; Hodel, Florian Journal of the American Chemical Society, Vol. 137, Issue 34 https://doi.org/10.1021/jacs.5b05831	journal	August 2015
Electocatalytic Water Oxidation by Cobalt(III) Hangman β-Octafluoro Corroles Dogutan, Dilek K.; McGuire, Robert; Nocera, Daniel G. Journal of the American Chemical Society, Vol. 133, Issue 24 https://doi.org/10.1021/ja202138m	journal	June 2011
Evidence for holes on oxygen in some nickel oxides Rao, G. Ranga; Hegde, M. S.; Sarma, D. D. Journal of Physics: Condensed Matter, Vol. 1, Issue 11 https://doi.org/10.1088/0953-8984/1/11/026	journal	March 1989
Changes in electronic structure by Li ion deintercalation in LiNiO2 from nickel L-edge and O K-edge XANES Uchimoto, Yoshiharu; Sawada, Hiroshi; Yao, Takeshi Journal of Power Sources, Vol. 97-98 https://doi.org/10.1016/S0378-7753(01)00624-3	journal	July 2001
Character of Holes in ${Li}_{x} {Ni}_{1 - x} O$ and Their Magnetic Behavior Kuiper, P.; Kruizinga, G.; Ghijsen, J. Physical Review Letters, Vol. 62, Issue 2 https://doi.org/10.1103/PhysRevLett.62.221	journal	January 1989
Role of Oxygen Holes in ${Li}_{x} {CoO}_{2}$ Revealed by Soft X-Ray Spectroscopy Mizokawa, T.; Wakisaka, Y.; Sudayama, T. Physical Review Letters, Vol. 111, Issue 5 https://doi.org/10.1103/PhysRevLett.111.056404	journal	August 2013
Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen Luo, Kun; Roberts, Matthew R.; Hao, Rong Nature Chemistry, Vol. 8, Issue 7 https://doi.org/10.1038/nchem.2471	journal	March 2016

Cited By (15)

Ein aktiver und stabiler Cobaltkatalysator für die Sauerstoffentwicklungsreaktion: Polymerisation einer ionischen Flüssigkeit Ding, Yuxiao; Klyushin, Alexander; Huang, Xing Angewandte Chemie, Vol. 130, Issue 13 https://doi.org/10.1002/ange.201711688	journal	February 2018
The Role of Supported Atomically Distributed Metal Species in Electrochemistry and How to Create Them Ding, Yuxiao; Schlögl, Robert; Heumann, Saskia ChemElectroChem, Vol. 6, Issue 15 https://doi.org/10.1002/celc.201900598	journal	May 2019
A multifunctional vanadium-doped cobalt oxide layer on silicon photoanodes for efficient and stable photoelectrochemical water oxidation Xing, Zhuo; Wu, Hengyi; Wu, Liang Journal of Materials Chemistry A, Vol. 6, Issue 42 https://doi.org/10.1039/c8ta07552b	journal	January 2018
Directly Electrodeposited Cobalt Sulfide Nanosheets as Advanced Catalyst for Oxygen Evolution Reaction Nan, Kaikai; Du, Hongfang; Su, Lan ChemistrySelect, Vol. 3, Issue 25 https://doi.org/10.1002/slct.201801482	journal	July 2018
Significance of hydrogen bonding networks in the proton-coupled electron transfer reactions of photosystem II from a quantum-mechanics perspective Chai, Jun; Zheng, Zhaoyang; Pan, Hui Physical Chemistry Chemical Physics, Vol. 21, Issue 17 https://doi.org/10.1039/c9cp00868c	journal	January 2019
Cobalt-Bridged Ionic Liquid Polymer on a Carbon Nanotube for Enhanced Oxygen Evolution Reaction Activity Ding, Yuxiao; Klyushin, Alexander; Huang, Xing Angewandte Chemie International Edition, Vol. 57, Issue 13 https://doi.org/10.1002/anie.201711688	journal	February 2018
MnO ₂ /MnCo ₂ O ₄ /Ni heterostructure with quadruple hierarchy: a bifunctional electrode architecture for overall urea oxidation Xiao, Changlong; Li, Shuni; Zhang, Xinyi Journal of Materials Chemistry A, Vol. 5, Issue 17 https://doi.org/10.1039/c7ta00980a	journal	January 2017
Synthesis and reactivity of a mononuclear non-haem cobalt(IV)-oxo complex Wang, Bin; Lee, Yong-Min; Tcho, Woon-Young Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14839	journal	March 2017
2D Metal Organic Framework‐Graphitic Carbon Nanocomposites as Precursors for High‐Performance O ₂ ‐Evolution Electrocatalysts Rodenas, Tania; Beeg, Sebastian; Spanos, Ioannis Advanced Energy Materials, Vol. 8, Issue 35 https://doi.org/10.1002/aenm.201802404	journal	October 2018
Selective C(sp ² )‐H Amination Catalyzed by High‐Valent Cobalt(III)/(IV)‐bpy Complex Immobilized on Silica Nanoparticles Budnikova, Yulia; Bochkova, Olga; Khrizanforov, Mikhail ChemCatChem, Vol. 11, Issue 22 https://doi.org/10.1002/cctc.201901391	journal	October 2019
A cocoon silk chemistry strategy to ultrathin N-doped carbon nanosheet with metal single-site catalysts Zhu, Youqi; Sun, Wenming; Luo, Jun Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-06296-w	journal	September 2018
Operando X-Ray Absorption Spectroscopy Shows Iron Oxidation Is Concurrent with Oxygen Evolution in Cobalt-Iron (Oxy)hydroxide Electrocatalysts Enman, Lisa J.; Stevens, Michaela Burke; Dahan, Meir Haim Angewandte Chemie International Edition, Vol. 57, Issue 39 https://doi.org/10.1002/anie.201808818	journal	September 2018
Tuning oxygen vacancies in two-dimensional iron-cobalt oxide nanosheets through hydrogenation for enhanced oxygen evolution activity Zhuang, Linzhou; Jia, Yi; He, Tianwei Nano Research, Vol. 11, Issue 6 https://doi.org/10.1007/s12274-018-2050-8	journal	May 2018
Reactive Cobalt–Oxo Complexes of Tetrapyrrolic Macrocycles and N-based Ligand in Oxidative Transformation Reactions Ali, Atif; Akram, Waseem; Liu, Hai-Yang Molecules, Vol. 24, Issue 1 https://doi.org/10.3390/molecules24010078	journal	December 2018
Operando X‐Ray Absorption Spectroscopy Shows Iron Oxidation Is Concurrent with Oxygen Evolution in Cobalt–Iron (Oxy)hydroxide Electrocatalysts Enman, Lisa J.; Stevens, Michaela Burke; Dahan, Meir Haim Angewandte Chemie, Vol. 130, Issue 39 https://doi.org/10.1002/ange.201808818	journal	September 2018

Similar Records

Synthetic control and empirical prediction of redox potentials for Co₄O₄ cubanes over a 1.4 V range: implications for catalyst design and evaluation of high-valent intermediates in water oxidation

Journal Article · Fri Apr 07 00:00:00 EDT 2017 · Chemical Science · OSTI ID:1339577

Nguyen, Andy I.; Wang, Jianing; Levine, Daniel S.; +2 more

Crystal Structure and C–H Bond-Cleaving Reactivity of a Mononuclear Co^IV–Dinitrate Complex

Journal Article · Wed Jul 08 00:00:00 EDT 2020 · Journal of the American Chemical Society · OSTI ID:1339577

Kwon, Yubin M.; Lee, Yuri; Evenson, Garrett E.; +2 more

In situ characterization of cofacial Co(IV) centers in Co₄O₄ cubane: Modeling the high-valent active site in oxygen-evolving catalysts

Journal Article · Mon Mar 27 00:00:00 EDT 2017 · Proceedings of the National Academy of Sciences of the United States of America · OSTI ID:1339577

Brodsky, Casey N.; Hadt, Ryan G.; Hayes, Dugan; +4 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: X-ray spectroscopic characterization of Co(IV) and metal–metal interactions in Co4O4: Electronic structure contributions to the formation of high-valent states relevant to the oxygen evolution reaction

Citation Formats

References (108)

Cited By (15)

Similar Records

Related Subjects

Title: X-ray spectroscopic characterization of Co(IV) and metal–metal interactions in Co₄O₄: Electronic structure contributions to the formation of high-valent states relevant to the oxygen evolution reaction