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Unraveling Nanoscale Cobalt Oxide Catalysts for the Oxygen Evolution Reaction: Maximum Performance, Minimum Effort

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    Unraveling Nanoscale Cobalt Oxide Catalysts for the Oxygen Evolution Reaction: Maximum Performance, Minimum Effort
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2021, 143, 37, 15022–15038
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    https://doi.org/10.1021/jacs.1c03375
    Published September 9, 2021
    Copyright © 2021 American Chemical Society
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    Abstract

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    The oxygen evolution reaction (OER) is a key bottleneck step of artificial photosynthesis and an essential topic in renewable energy research. Therefore, stable, efficient, and economical water oxidation catalysts (WOCs) are in high demand and cobalt-based nanomaterials are promising targets. Herein, we tackle two key open questions after decades of research into cobalt-assisted visible-light-driven water oxidation: What makes simple cobalt-based precipitates so highly active—and to what extent do we need Co-WOC design? Hence, we started from Co(NO3)2 to generate a precursor precipitate, which transforms into a highly active WOC during the photocatalytic process with a [Ru(bpy)3]2+/S2O82–/borate buffer standard assay that outperforms state of the art cobalt catalysts. The structural transformations of these nanosized Co catalysts were monitored with a wide range of characterization techniques. The results reveal that the precipitated catalyst does not fully change into an amorphous CoOx material but develops some crystalline features. The transition from the precipitate into a disordered Co3O4 material proceeds within ca. 1 min, followed by further transformation into highly active disordered CoOOH within the first 10 min. Furthermore, under noncatalytic conditions, the precursor directly transforms into CoOOH. Moreover, fast precipitation and isolation afford a highly active precatalyst with an exceptional O2 yield of 91% for water oxidation with the visible-light-driven [Ru(bpy)3]2+/S2O82– assay, which outperforms a wide range of carefully designed Co-containing WOCs. We thus demonstrate that high-performance cobalt-based OER catalysts indeed emerge effortlessly from a self-optimization process favoring the formation of Co(III) centers in all-octahedral environments. This paves the way to new low-maintenance flow chemistry OER processes.

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.1c03375.

    • Literature survey of reference catalysts, PXRD patterns for catalysts obtained under “Standard” and various additional conditions, ICP-MS data of the Co, B, and S contents and CHN elemental analyses for representative samples, PXRD and FT-IR data for normal/extended separation processes, TEM images of Co catalysts, DLS measurements of the sample Standard-L-10min, SAXS size distribution plots for different time intervals (before irradiation, 1 min, 30 min, 60 min, 2 h, 11 h, 24 h), FT-IR spectroscopic data of catalysts under different precipitation conditions and for postcatalytic measurements, Co valence state calculations at μ(E) values of 0.5 and 0.8, EXAFS fitting of the experimental Co K-edge spectra k3χ(k) and fitting parameters for various samples, Clark electrode measurements up to 21 min, EDX characterization of a postcatalytic sample, and PXRD pattern of the reference Co4-POM (PDF)

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    Cited By

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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2021, 143, 37, 15022–15038
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.1c03375
    Published September 9, 2021
    Copyright © 2021 American Chemical Society
    Request reuse permissions

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