Yelena Gorlin

There is a growing interest in oxygen electrochemistry as conversions between O(2) and H(2)O play an important role in a variety of renewable energy technologies. The goal of this work is to develop active bifunctional catalyst materials for water oxidation and oxygen reduction. Drawing inspiration from a cubane-like CaMn(4)O(x), the biological catalyst found in the oxygen evolving center (OEC) in photosystem II, nanostructured manganese oxide surfaces were investigated for these reactions. Thin films of nanostructured manganese oxide were found to be active for both oxygen reduction and water oxidation, with similar overall oxygen electrode activity to the best known precious metal nanoparticle catalysts: platinum, ruthenium, and iridium. Physical and chemical characterization of the nanostructured Mn oxide bifunctional catalyst reveals an oxidation state of Mn(III), akin to one of the most commonly observed Mn oxidation states found in the OEC.

In situ X-ray absorption spectroscopy (XAS) is a powerful technique that can be applied to electrochemical systems, with the ability to elucidate the chemical nature of electrocatalysts under reaction conditions. In this study, we perform in situ XAS measurements on a bifunctional manganese oxide (MnOx) catalyst with high electrochemical activity for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Using X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), we find that exposure to an ORR-relevant potential of 0.7 V vs RHE produces a disordered Mn3(II,III,III)O4 phase with negligible contributions from other phases. After the potential is increased to a highly anodic value of 1.8 V vs RHE, relevant to the OER, we observe an oxidation of approximately 80% of the catalytic thin film to form a mixed Mn(III,IV) oxide, while the remaining 20% of the film consists of a less oxidized phase, likely corresponding to unchanged Mn3(II,III,III)O4. XAS and electrochemical characterization of two thin film catalysts with different MnOx thicknesses reveals no significant influence of thickness on the measured oxidation states, at either ORR or OER potentials, but demonstrates that the OER activity scales with film thickness. This result suggests that the films have porous structure, which does not restrict electrocatalysis to the top geometric layer of the film. As the portion of the catalyst film that is most likely to be oxidized at the high potentials necessary for the OER is that which is closest to the electrolyte interface, we hypothesize that the Mn(III,IV) oxide, rather than Mn3(II,III,III)O4, is the phase pertinent to the observed OER activity.

Progress in the field of electrocatalysis is often hampered by the difficulty in identifying the active site on an electrode surface. Herein we combine theoretical analysis and electrochemical methods to identify the active surfaces in a manganese oxide bi-functional catalyst for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). First, we electrochemically characterize the nanostructured α-Mn(2)O(3) and find that it undergoes oxidation in two potential regions: initially, between 0.5 V and 0.8 V, a potential region relevant to the ORR and, subsequently, between 0.8 V and 1.0 V, a potential region between the ORR and the OER relevant conditions. Next, we perform density function theory (DFT) calculations to understand the changes in the MnO(x) surface as a function of potential and to elucidate reaction mechanisms that lead to high activities observed in the experiments. Using DFT, we construct surface Pourbaix and free energy diagrams of three different MnO(x) surfaces and identify 1/2 ML HO* covered Mn(2)O(3) and O* covered MnO(2), as the active surfaces for the ORR and the OER, respectively. Additionally, we find that the ORR occurs through an associative mechanism and that its overpotential is highly dependent on the stabilization of intermediates through hydrogen bonds with water molecules. We also determine that OER occurs through direct recombination mechanism and that its major source of overpotential is the scaling relationship between HOO* and HO* surface intermediates. Using a previously developed Sabatier model we show that the theoretical predictions of catalytic activities match the experimentally determined onset potentials for the ORR and the OER, both qualitatively and quantitatively. Consequently, the combination of first-principles theoretical analysis and experimental methods offers an understanding of manganese oxide oxygen electrocatalysis at the atomic level, achieving fundamental insight that can potentially be used to design and develop improved electrocatalysts for the ORR and the OER and other important reactions of technological interest.

Abstract The ability to deposit conformal catalytic thin films enables opportunities to achieve complex nanostructured designs for catalysis. Atomic layer deposition (ALD) is capable of creating conformal thin films over complex substrates. Here, ALD‐MnO x on glassy carbon is investigated as a catalyst for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR), two reactions that are of growing interest due to their many applications in alternative energy technologies. The films are characterized by X‐ray photoelectron spectroscopy, X‐ray diffraction, scanning electron microscopy, ellipsometry, and cyclic voltammetry. The as‐deposited films consist of Mn(II)O, which is shown to be a poor catalyst for the ORR, but highly active for the OER. By controllably annealing the samples, Mn 2 O 3 catalysts with good activity for both the ORR and OER are synthesized. Hypotheses are presented to explain the large difference in the activity between the MnO and Mn 2 O 3 catalysts for the ORR, but similar activity for the OER, including the effects of surface oxidation under experimental conditions. These catalysts synthesized though ALD compare favorably to the best MnO x catalysts in the literature, demonstrating a viable way to produce highly active, conformal thin films from earth‐abundant materials for the ORR and the OER.

<italic>Operando</italic> X-ray absorption spectroscopy studies of transition metal dissolution in Li-ion batteries.