earned a B.S. degree in chemistry from the University of Dayton in 2001 and as an undergraduate worked on conductive polymer syntheses at the Air Force Research Laboratory at Wright Patterson Air Force Base. He completed an M.S. degree in 2004 and Ph.D. degree in 2008 at Portland State University and joined the Lewis group at Caltech in 2008. He is currently an NSF-ACCF postdoctoral fellow (2009) and has been studying the electrical characteristics of inorganic semiconductors in contact with conductive polymers. His research interests include molecular semiconductors for solar energy conversion, porphyrin macrocycles for optoelectronic applications, and catalyst materials for photoelectrolysis. Emily L. Warren received a B.S. in chemical engineering at Cornell University in 2005. She received an M.Phil in Engineering for Sustainable Development from Cambridge University in 2006. She is currently a graduate student in Chemical Engineering at the California Institute of Technology. Her research interests include semiconductor photoelectrochemistry, solar energy conversion, and semiconductor nanowires. She is currently a graduate student in Chemical Engineering at the California Institute of Technology, working under Nathan S. Lewis. James R. McKone is in his third year of graduate studies in the Division of Chemistry and Chemical Engineering at the California Institute of Technology, working under Nathan S. Lewis and Harry B. Gray. In 2008 he graduated from Saint Olaf College with a Bachelor of Arts degree, double-majoring in music and chemistry. His current research focuses on semiconductor-coupled heterogeneous catalysis of the hydrogen evolution reaction using mixtures of earth-abundant transition metals. Shannon W. Boettcher earned his B.A. degree in chemistry from the University of Oregon, Eugene (2003), and, working with Galen Stucky, his Ph.D. in Inorganic Chemistry from the University of California, Santa Barbara (2008). Following postdoctoral work with Nate Lewis and Harry Atwater at the California Institute of Technology (2008-2010), he returned to the University of Oregon to join the faculty as an Assistant Professor. His research interests span synthesis and physical measurement with the goal of designing and understanding solid-state inorganic material architectures for use in solar-energy conversion and storage.

Fe plays a critical, but not yet understood, role in enhancing the activity of the Ni-based oxygen evolution reaction (OER) electrocatalysts. We report electrochemical, in situ electrical, photoelectron spectroscopy, and X-ray diffraction measurements on Ni(1-x)Fe(x)(OH)2/Ni(1-x)Fe(x)OOH thin films to investigate the changes in electronic properties, OER activity, and structure as a result of Fe inclusion. We developed a simple method for purification of KOH electrolyte that uses precipitated bulk Ni(OH)2 to absorb Fe impurities. Cyclic voltammetry on rigorously Fe-free Ni(OH)2/NiOOH reveals new Ni redox features and no significant OER current until >400 mV overpotential, different from previous reports which were likely affected by Fe impurities. We show through controlled crystallization that β-NiOOH is less active for OER than the disordered γ-NiOOH starting material and that previous reports of increased activity for β-NiOOH are due to incorporation of Fe-impurities during the crystallization process. Through-film in situ conductivity measurements show a >30-fold increase in film conductivity with Fe addition, but this change in conductivity is not sufficient to explain the observed changes in activity. Measurements of activity as a function of film thickness on Au and glassy carbon substrates are consistent with the hypothesis that Fe exerts a partial-charge-transfer activation effect on Ni, similar to that observed for noble-metal electrode surfaces. These results have significant implications for the design and study of Ni(1-x)Fe(x)OOH OER electrocatalysts, which are the fastest measured OER catalysts under basic conditions.

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.

Water oxidation is a critical step in water splitting to make hydrogen fuel. We report the solution synthesis, structural/compositional characterization, and oxygen evolution reaction (OER) electrocatalytic properties of ~2-3 nm thick films of NiO(x), CoO(x), Ni(y)Co(1-y)O(x), Ni(0.9)Fe(0.1)O(x), IrO(x), MnO(x), and FeO(x). The thin-film geometry enables the use of quartz crystal microgravimetry, voltammetry, and steady-state Tafel measurements to study the electrocatalytic activity and electrochemical properties of the oxides. Ni(0.9)Fe(0.1)O(x) was found to be the most active water oxidation catalyst in basic media, passing 10 mA cm(-2) at an overpotential of 336 mV with a Tafel slope of 30 mV dec(-1) with oxygen evolution reaction (OER) activity roughly an order of magnitude higher than IrO(x) control films and similar to the best known OER catalysts in basic media. The high activity is attributed to the in situ formation of layered Ni(0.9)Fe(0.1)OOH oxyhydroxide species with nearly every Ni atom electrochemically active. In contrast to previous reports that showed synergy between Co and Ni oxides for OER catalysis, Ni(y)Co(1-y)O(x) thin films showed decreasing activity relative to the pure NiO(x) films with increasing Co content. This finding is explained by the suppressed in situ formation of the active layered oxyhydroxide with increasing Co. The high OER activity and simple synthesis make these Ni-based catalyst thin films useful for incorporating with semiconductor photoelectrodes for direct solar-driven water splitting or in high-surface-area electrodes for water electrolysis.

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