Cobalt-iron (oxy)hydroxide oxygen evolution electrocatalysts: the role of structure and composition on activity, stability, and mechanism

J Am Chem Soc. 2015 Mar 18;137(10):3638-48. doi: 10.1021/jacs.5b00281. Epub 2015 Mar 4.


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 Co(1-x)Fe(x)(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 Co(2+/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 Co(1-x)Fe(x)(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.