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.

Poor oxygen evolution reaction (OER) catalysis limits the efficiency of H2 production from water electrolysis and photoelectrolysis routes to large-scale energy storage. Despite nearly a century of research, the factors governing the activity of OER catalysts are not well understood. In this Perspective, we discuss recent advances in understanding the OER in alkaline media for earth-abundant, first-row, transition-metal oxides and (oxy)­hydroxides. We argue that the most-relevant structures for study are thermodynamically stable (oxy)­hydroxides and not crystalline oxides. We discuss thin-film electrochemical microbalance techniques to accurately quantify intrinsic activity and in situ conductivity measurements to identify materials limited by electronic transport. We highlight the dramatic effect that Fe cationsadded either intentionally or unintentionally from ubiquitous electrolyte impuritieshave on the activity of common OER catalysts. We find new activity trends across the first-row transition metals, opposite of the established ones, and propose a new view of OER on mixed-metal (oxy)­hydroxides that illustrates possible design principles and applications.

First-row transition-metal oxides and (oxy)hydroxides catalyze the oxygen evolution reaction (OER) in alkaline media. Understanding the intrinsic catalytic activity provides insight into improved catalyst design. Experimental and computationally predicted activity trends, however, have varied substantially. Here we describe a new OER activity trend for nominally oxyhydroxide thin films of Ni(Fe)O(x)H(y) > Co(Fe)O(x)H(y) > FeO(x)H(y)-AuO(x) > FeO(x)H(y) > CoO(x)H(y) > NiO(x)H(y) > MnO(x)H(y). This intrinsic trend has been previously obscured by electrolyte impurities, potential-dependent electrical conductivity, and difficulty in correcting for surface-area or mass-loading differences. A quartz-crystal microbalance was used to monitor mass in situ and X-ray photoelectron spectroscopy to measure composition and impurity levels. These new results provide a basis for comparison to theory and help guide the design of improved catalyst systems.

Fe cations dramatically enhance oxygen evolution reaction (OER) activity when incorporated substitutionally into Ni or Co (oxy)hydroxides, serving as possible OER active sites. Pure Fe (oxy)hydroxides, however, are typically thought to be poor OER catalysts and are not well-understood. Here, we report a systematic investigation of Fe (oxy)hydroxide OER catalysis in alkaline media. At low overpotentials of ∼350 mV, the catalyst dissolution rate is low, the activity is dramatically enhanced by an AuO x /Au substrate, and the geometric OER current density is largely independent of mass loading. At higher overpotentials of ∼450 mV, the dissolution rate is high, the activity is largely independent of substrate choice, and the geometric current density depends linearly on loading. These observations, along with previously reported in situ conductivity measurements, suggest a new model for OER catalysis on Fe (oxy)hydroxide. At low overpotentials, only the first monolayer of the electrolyte-permeable Fe (oxy)hydroxide, which is in direct contact with the conductive support, is OER-active due to electrical conductivity limitations. On Au substrates, Fe cations interact with AuO x after redox cycling, leading to enhanced intrinsic activity over FeOOH on Pt substrates. At higher overpotentials, the conductivity of Fe (oxy)hydroxide increases, leading to a larger fraction of the electrolyte-permeable catalyst film participating in catalysis. Comparing the apparent activity of the putative Fe active sites in/on different hosts/surfaces supports a possible connection between OER activity and local structure.

Fe-doped Ni (oxy)hydroxide, Ni(Fe)O x H y , is one of the most-active oxygen-evolution-reaction (OER) catalysts in alkaline conditions, while Fe-free NiO x H y is a poor OER catalyst. One approach to better understand the role of Fe, and enable the design of catalysts with higher activities, is to find other cations that behave similarly and compare the common chemical features between them. Here we evaluate the effects of La, Mn, Ce, and Ti incorporation on the OER activity and redox behavior of NiO x H y in rigorously Fe-free alkaline solution using cyclic voltammetry and electrochemical quartz-crystal microgravimetry. We use X-ray photoelectron spectroscopy and time-of-flight secondary-ionmass spectrometry to confirm that measurements are free from relevant levels of trace Fe contamination. We find that only Ce leads to increased activity in NiO x H y (about a factor of 10 enhancement), but this effect is transient, likely due to phase separation. We further find no clear correlation between activity and the nominal Ni 2+/3+ redox potential, suggesting that the "oxidizing" power of the Ni is not directly correlated with the OER activity. These findings suggest a uniqueness to Fe and are consistent with it being the active site in Ni(Fe)O x H y .

Ni-borate materials are oxygen evolution catalysts that operate at near-neutral pH and have been found previously to improve due to structural changes induced via anodic conditioning. We find that this increased activity after conditioning at 0.856 V vs. SCE, as measured on a turn-over frequency basis (TOF) at 400 mV overpotential (TOF = 0.38 s(-1)), accompanies significant Fe incorporation (14%). Films conditioned in Fe-free electrolyte exhibit ∼10 times lower activity (TOF = 0.03 s(-1)). By co-depositing Fe-Ni we demonstrate high activity without conditioning (TOF = 0.24 s(-1)) which improves further with shortened (∼30 min) conditioning (TOF = 1.4 s(-1)).

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