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Cobalt–Iron (Oxy)hydroxide Oxygen Evolution Electrocatalysts: The Role of Structure and Composition on Activity, Stability, and Mechanism

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Burke, Michaela S., Kast, Matthew G., Trotochaud, Lena, Smith, Adam M., Boettcher, Shannon W.·2015·Journal of the American Chemical Society
DOI 10.1021/jacs.5b00281
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Abstract

Cobalt oxides and (oxy)hydroxides have been widely studied as electrocatalysts for the oxygen evolution reaction (OER). For related Ni-based materials, the addition of Fe dramatically enhances OER activity. The role of Fe in Co-based materials is not well-documented. We show that the intrinsic OER activity of Co1–xFex(OOH) is ∼100-fold higher for x ≈ 0.6–0.7 than for x = 0 on a per-metal turnover frequency basis. Fe-free CoOOH absorbs Fe from electrolyte impurities if the electrolyte is not rigorously purified. Fe incorporation and increased activity correlate with an anodic shift in the nominally Co2+/3+ redox wave, indicating strong electronic interactions between the two elements and likely substitutional doping of Fe for Co. In situ electrical measurements show that Co1–xFex(OOH) is conductive under OER conditions (∼0.7–4 mS cm–1 at ∼300 mV overpotential), but that FeOOH is an insulator with measurable conductivity (2.2 × 10–2 mS cm–1) only at high overpotentials >400 mV. The apparent OER activity of FeOOH is thus limited by low conductivity. Microbalance measurements show that films with x ≥ 0.54 (i.e., Fe-rich) dissolve in 1 M KOH electrolyte under OER conditions. For x < 0.54, the films appear chemically stable, but the OER activity decreases by 16–62% over 2 h, likely due to conversion into denser, oxide-like phases. We thus hypothesize that Fe is the most-active site in the catalyst, while CoOOH primarily provides a conductive, high-surface area, chemically stabilizing host. These results are important as Fe-containing Co- and Ni-(oxy)hydroxides are the fastest OER catalysts known.

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Metadata

Authors
Burke, M. S., Kast, M. G., Trotochaud, L., Smith, A. M., & Boettcher, S. W.
Venue
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Published
2015-02-20
Volume
137
Issue
10
Pages
3638-3648
ISSN
  • 0002-7863 (ISSN-L)
  • 1520-5126
DOI
10.1021/jacs.5b00281
OpenAlex
W2018624132
Cited by
1,972
References
1
FWCI
50.15
Type
journal article
Language
en
Open access
hybrid
Licence
pubs.acs.org/page/policy/authorchoice_termsofuse.html (vor, 12 d)
Funders
  • Division of Chemistry (CHE-1301461)
  • Research Corporation for Science Advancement (NA)

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CoChat. (2026). Citation check: Cobalt–Iron (Oxy)hydroxide Oxygen Evolution Electrocatalysts: The Role of Structure and Composition on Activity, Stability, and Mechanism. https://app.cochat.ai/papers/10.1021/jacs.5b00281
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Burke, M. S., Kast, M. G., Trotochaud, L., Smith, A. M., & Boettcher, S. W. (2015). Cobalt–Iron (Oxy)hydroxide Oxygen Evolution Electrocatalysts: The Role of Structure and Composition on Activity, Stability, and Mechanism. Journal of the American Chemical Society. https://doi.org/10.1021/jacs.5b00281

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