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Title: 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

Abstract

The oxo-cobalt cubane unit [Co4O4] is of interest as a homogeneous oxygen-evolution reaction (OER) catalyst, and as a functional mimic of heterogeneous cobalt oxide OER catalysts. The synthesis of several new cubanes allows evaluation of redox potentials for the [Co4O4] cluster, which are highly sensitive to the ligand environment and span a remarkable range of 1.42 V. The [CoIII4O4]4+/[CoIII3CoIVO4]5+ and [CoIII3CoIVO4]5+/[CoIII2CoIV2O4]6+ redox potentials are reliably predicted by the pKas of the ligands. Hydrogen bonding is also shown to significantly raise the redox potentials, by ~500 mV. The potential-pKa correlation is used to evaluate the feasibility of various proposed OER catalytic intermediates, including high-valent Co-oxo species. The synthetic methods and structure–reactivity relationships developed by these studies should better guide the design of new cubane-based OER catalysts.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [1];  [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1379637
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 8; Journal Issue: 6; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Nguyen, Andy I., Wang, Jianing, Levine, Daniel S., Ziegler, Micah S., and Tilley, T. Don. 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. United States: N. p., 2017. Web. doi:10.1039/c7sc00627f.
Nguyen, Andy I., Wang, Jianing, Levine, Daniel S., Ziegler, Micah S., & Tilley, T. Don. 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. United States. doi:10.1039/c7sc00627f.
Nguyen, Andy I., Wang, Jianing, Levine, Daniel S., Ziegler, Micah S., and Tilley, T. Don. Fri . "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". United States. doi:10.1039/c7sc00627f. https://www.osti.gov/servlets/purl/1379637.
@article{osti_1379637,
title = {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},
author = {Nguyen, Andy I. and Wang, Jianing and Levine, Daniel S. and Ziegler, Micah S. and Tilley, T. Don},
abstractNote = {The oxo-cobalt cubane unit [Co4O4] is of interest as a homogeneous oxygen-evolution reaction (OER) catalyst, and as a functional mimic of heterogeneous cobalt oxide OER catalysts. The synthesis of several new cubanes allows evaluation of redox potentials for the [Co4O4] cluster, which are highly sensitive to the ligand environment and span a remarkable range of 1.42 V. The [CoIII4O4]4+/[CoIII3CoIVO4]5+ and [CoIII3CoIVO4]5+/[CoIII2CoIV2O4]6+ redox potentials are reliably predicted by the pKas of the ligands. Hydrogen bonding is also shown to significantly raise the redox potentials, by ~500 mV. The potential-pKa correlation is used to evaluate the feasibility of various proposed OER catalytic intermediates, including high-valent Co-oxo species. The synthetic methods and structure–reactivity relationships developed by these studies should better guide the design of new cubane-based OER catalysts.},
doi = {10.1039/c7sc00627f},
journal = {Chemical Science},
number = 6,
volume = 8,
place = {United States},
year = {2017},
month = {4}
}

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Cited by: 11 works
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Works referenced in this record:

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    Works referencing / citing this record:

    Preparation and Properties of a Monomeric High-Spin Mn V –Oxo Complex
    journal, January 2012

    • Taguchi, Taketo; Gupta, Rupal; Lassalle-Kaiser, Benedikt
    • Journal of the American Chemical Society, Vol. 134, Issue 4
    • DOI: 10.1021/ja210957u

    Reaction Pathways for Water Oxidation to Molecular Oxygen Mediated by Model Cobalt Oxide Dimer and Cubane Catalysts
    journal, January 2015

    • Fernando, Amendra; Aikens, Christine M.
    • The Journal of Physical Chemistry C, Vol. 119, Issue 20
    • DOI: 10.1021/jp511805x

    Synthetic model of the asymmetric [Mn3CaO4] cubane core of the oxygen-evolving complex of photosystem II
    journal, January 2012

    • Mukherjee, S.; Stull, J. A.; Yano, J.
    • Proceedings of the National Academy of Sciences, Vol. 109, Issue 7
    • DOI: 10.1073/pnas.1115290109

    Mixed-valence, tetranuclear cobalt(iii,iv) complexes: preparation and properties of [Co4O4(O2CR)2(bpy)4]3+ salts
    journal, January 2001

    • Dimitrou, Katerina; Brown, Angelica D.; Christou, George
    • Chemical Communications, Issue 14
    • DOI: 10.1039/b102008k

    Direct-Coupling O 2 Bond Forming a Pathway in Cobalt Oxide Water Oxidation Catalysts
    journal, August 2011

    • Wang, Lee-Ping; Van Voorhis, Troy
    • The Journal of Physical Chemistry Letters, Vol. 2, Issue 17
    • DOI: 10.1021/jz201021n

    Electrochemical Water Oxidation with Cobalt-Based Electrocatalysts from pH 0–14: The Thermodynamic Basis for Catalyst Structure, Stability, and Activity
    journal, August 2011

    • Gerken, James B.; McAlpin, J. Gregory; Chen, Jamie Y. C.
    • Journal of the American Chemical Society, Vol. 133, Issue 36
    • DOI: 10.1021/ja205647m

    Water Oxidation by the [Co 4 O 4 (OAc) 4 (py) 4 ] + Cubium is Initiated by OH Addition
    journal, December 2015

    • Smith, Paul F.; Hunt, Liam; Laursen, Anders B.
    • Journal of the American Chemical Society, Vol. 137, Issue 49
    • DOI: 10.1021/jacs.5b09152

    Water oxidation chemistry of photosystem II
    journal, October 2007

    • Brudvig, Gary W.
    • Philosophical Transactions of the Royal Society B: Biological Sciences, Vol. 363, Issue 1494
    • DOI: 10.1098/rstb.2007.2217

    Complexation of 7-azaindole by the methylmercury(II) cation
    journal, December 1992

    • Dufour, Nathalie; Lebuis, Anne-Marie; Corbeil, Marie-Claude
    • Canadian Journal of Chemistry, Vol. 70, Issue 12
    • DOI: 10.1139/v92-373

    Photocatalytic Water Oxidation: Tuning Light-Induced Electron Transfer by Molecular Co 4 O 4 Cores
    journal, June 2012

    • Berardi, Serena; La Ganga, Giuseppina; Natali, Mirco
    • Journal of the American Chemical Society, Vol. 134, Issue 27
    • DOI: 10.1021/ja303951z

    Mechanisms of Water Oxidation from the Blue Dimer to Photosystem II
    journal, March 2008

    • Liu, Feng; Concepcion, Javier J.; Jurss, Jonah W.
    • Inorganic Chemistry, Vol. 47, Issue 6
    • DOI: 10.1021/ic701249s

    Electrocatalytic Water Oxidation by a Dinuclear Copper Complex in a Neutral Aqueous Solution
    journal, February 2015

    • Su, Xiao-Jun; Gao, Meng; Jiao, Lei
    • Angewandte Chemie International Edition, Vol. 54, Issue 16
    • DOI: 10.1002/anie.201411625

    Synthesis, Structure, Spectral and Electrochemical Properties, and Catalytic Use of Cobalt(III)−Oxo Cubane Clusters
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    • Chakrabarty, Rajesh; Bora, Sanchay J.; Das, Birinchi K.
    • Inorganic Chemistry, Vol. 46, Issue 22
    • DOI: 10.1021/ic7011759

    Efficient water oxidation catalysts based on readily available iron coordination complexes
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    • Fillol, Julio Lloret; Codolà, Zoel; Garcia-Bosch, Isaac
    • Nature Chemistry, Vol. 3, Issue 10
    • DOI: 10.1038/nchem.1140

    Water Oxidation Catalysis by Co(II) Impurities in Co(III) 4 O 4 Cubanes
    journal, December 2014

    • Ullman, Andrew M.; Liu, Yi; Huynh, Michael
    • Journal of the American Chemical Society, Vol. 136, Issue 50
    • DOI: 10.1021/ja5110393

    A synthetic Mn4Ca-cluster mimicking the oxygen-evolving center of photosynthesis
    journal, May 2015


    Mechanistic Investigations of Water Oxidation by a Molecular Cobalt Oxide Analogue: Evidence for a Highly Oxidized Intermediate and Exclusive Terminal Oxo Participation
    journal, September 2015

    • Nguyen, Andy I.; Ziegler, Micah S.; Oña-Burgos, Pascual
    • Journal of the American Chemical Society, Vol. 137, Issue 40
    • DOI: 10.1021/jacs.5b08396

    Water Oxidation Mechanism for Synthetic Co–Oxides with Small Nuclearity
    journal, September 2013

    • Li, Xichen; Siegbahn, Per E. M.
    • Journal of the American Chemical Society, Vol. 135, Issue 37
    • DOI: 10.1021/ja4053448

    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
    • DOI: 10.1021/ja1013344

    A hydrogen-bonding network plays a catalytic role in photosynthetic oxygen evolution
    journal, April 2012

    • Polander, B. C.; Barry, B. A.
    • Proceedings of the National Academy of Sciences, Vol. 109, Issue 16
    • DOI: 10.1073/pnas.1200093109

    A molecular structural analog of proposed dinuclear active sites in cobalt-based water oxidation catalysts
    journal, January 2014

    • Davenport, Timothy C.; Ahn, Hyun S.; Ziegler, Micah S.
    • Chemical Communications, Vol. 50, Issue 48
    • DOI: 10.1039/c3cc46865h

    Conduction and Reactivity in Heterogeneous-Molecular Catalysis: New Insights in Water Oxidation Catalysis by Phosphate Cobalt Oxide Films
    journal, April 2016

    • Costentin, Cyrille; Porter, Thomas R.; Savéant, Jean-Michel
    • Journal of the American Chemical Society, Vol. 138, Issue 17
    • DOI: 10.1021/jacs.6b00737

    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
    • DOI: 10.1038/nchem.1874

    Ammonia Binds to the Dangler Manganese of the Photosystem II Oxygen-Evolving Complex
    journal, July 2015

    • Oyala, Paul H.; Stich, Troy A.; Debus, Richard J.
    • Journal of the American Chemical Society, Vol. 137, Issue 27
    • DOI: 10.1021/jacs.5b04768

    Closer to Photosystem II: A Co 4 O 4 Cubane Catalyst with Flexible Ligand Architecture
    journal, December 2013

    • Evangelisti, Fabio; Güttinger, Robin; Moré, René
    • Journal of the American Chemical Society, Vol. 135, Issue 50
    • DOI: 10.1021/ja4098302

    Probing Edge Site Reactivity of Oxidic Cobalt Water Oxidation Catalysts
    journal, March 2016

    • Ullman, Andrew M.; Brodsky, Casey N.; Li, Nancy
    • Journal of the American Chemical Society, Vol. 138, Issue 12
    • DOI: 10.1021/jacs.6b00762

    A Co 4 O 4 “Cubane” Water Oxidation Catalyst Inspired by Photosynthesis
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    • McCool, Nicholas S.; Robinson, David M.; Sheats, John E.
    • Journal of the American Chemical Society, Vol. 133, Issue 30
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    CCDC 1532027: Experimental Crystal Structure Determination: WAXBIJ : tetrakis(μ-oxo)-tetrakis(μ-trifluoroacetato)-tetrapyridine-tetra-cobalt
    dataset, February 2017


    Electronic Structure Description of a [Co(III) 3 Co(IV)O 4 ] Cluster: A Model for the Paramagnetic Intermediate in Cobalt-Catalyzed Water Oxidation
    journal, October 2011

    • McAlpin, J. Gregory; Stich, Troy A.; Ohlin, C. André
    • Journal of the American Chemical Society, Vol. 133, Issue 39
    • DOI: 10.1021/ja202320q

    Computational Modeling of Cobalt-Based Water Oxidation: Current Status and Future Challenges
    journal, April 2018