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

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    Mechanistic Investigations of Water Oxidation by a Molecular Cobalt Oxide Analogue: Evidence for a Highly Oxidized Intermediate and Exclusive Terminal Oxo Participation
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    † Department of Chemistry, University of California at Berkeley, Berkeley, California 94720-1460, United States
    ‡ Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
    § Department of Chemistry and Physics, University of Almería, Carretera de Sacramento s/n, 04120 Almería, Spain
    ∥ Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
    *[email protected]
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    Cite this: J. Am. Chem. Soc. 2015, 137, 40, 12865–12872
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    https://doi.org/10.1021/jacs.5b08396
    Published September 21, 2015
    Copyright © 2015 American Chemical Society
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    Artificial photosynthesis (AP) promises to replace society’s dependence on fossil energy resources via conversion of sunlight into sustainable, carbon-neutral fuels. However, large-scale AP implementation remains impeded by a dearth of cheap, efficient catalysts for the oxygen evolution reaction (OER). Cobalt oxide materials can catalyze the OER and are potentially scalable due to the abundance of cobalt in the Earth’s crust; unfortunately, the activity of these materials is insufficient for practical AP implementation. Attempts to improve cobalt oxide’s activity have been stymied by limited mechanistic understanding that stems from the inherent difficulty of characterizing structure and reactivity at surfaces of heterogeneous materials. While previous studies on cobalt oxide revealed the intermediacy of the unusual Co(IV) oxidation state, much remains unknown, including whether bridging or terminal oxo ligands form O2 and what the relevant oxidation states are. We have addressed these issues by employing a homogeneous model for cobalt oxide, the [Co(III)4] cubane (Co4O4(OAc)4py4, py = pyridine, OAc = acetate), that can be oxidized to the [Co(IV)Co(III)3] state. Upon addition of 1 equiv of sodium hydroxide, the [Co(III)4] cubane is regenerated with stoichiometric formation of O2. Oxygen isotopic labeling experiments demonstrate that the cubane core remains intact during this stoichiometric OER, implying that terminal oxo ligands are responsible for forming O2. The OER is also examined with stopped-flow UV–visible spectroscopy, and its kinetic behavior is modeled, to surprisingly reveal that O2 formation requires disproportionation of the [Co(IV)Co(III)3] state to generate an even higher oxidation state, formally [Co(V)Co(III)3] or [Co(IV)2Co(III)2]. The mechanistic understanding provided by these results should accelerate the development of OER catalysts leading to increasingly efficient AP systems.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.5b08396. CIF files can also be obtained free of charge from the Cambridge Crystallographic Data Centre under reference numbers CCDC-1054644, CCDC-1054645, and CCDC-1054646.

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    • X-ray crystallographic data for [1H]PF6·2H2O (CIF)

    • X-ray crystallographic data for [1]PF6 (CIF)

    • X-ray crystallographic data for [1H]OTs (CIF)

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    Cite this: J. Am. Chem. Soc. 2015, 137, 40, 12865–12872
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