Recent Insights into Manganese Oxides in Catalyzing Oxygen Reduction Kinetics

The sluggish kinetics of the oxygen reduction reaction (ORR) limit the efficiency of numerous oxygen-based energy conversion devices such as fuel cells and metal-air batteries. Among earth abundant catalysts, manganese-based oxides have the highest activities approaching that of precious metals. In this Review, we summarize and analyze literature findings to highlight key parameters that influence the catalysis of the ORR on manganese-based oxides, including the number of electrons transferred as well as specific and mass activities. These insights can help develop design guides for highly active ORR catalysts and shape future fundamental research to gain new knowledge regarding the molecular mechanism of ORR catalysis.National Science Foundation (U.S.). Materials Research Science and Engineering Centers (Program) (award number DMR- 0819762)Skoltech-MIT CenterNational Science Foundation (U.S.). Graduate Research Fellowship (Grant no. DGE-1122374)United States. Department of Energy. Office of Basic Energy Sciences (contract no. DE-AC02- 98CH10886

Insights into Electrochemical Reactions from Ambient Pressure Photoelectron Spectroscopy

The understanding of fundamental processes in the bulk and at the interfaces of electrochemical devices is a prerequisite for the development of new technologies with higher efficiency and improved performance. One energy storage scheme of great interest is splitting water to form hydrogen and oxygen gas and converting back to electrical energy by their subsequent recombination with only water as a byproduct. However, kinetic limitations to the rate of oxygen-based electrochemical reactions hamper the efficiency in technologies such as solar fuels, fuel cells, and electrolyzers. For these reactions, the use of metal oxides as electrocatalysts is prevalent due to their stability, low cost, and ability to store oxygen within the lattice. However, due to the inherently convoluted nature of electrochemical and chemical processes in electrochemical systems, it is difficult to isolate and study individual electrochemical processes in a complex system. Therefore, in situ characterization tools are required for observing related physical and chemical processes directly at the places where and while they occur and can help elucidate the mechanisms of charge separation and charge transfer at electrochemical interfaces.National Science Foundation (U.S.). Materials Research Science and Engineering Centers (Program)Skoltech-MIT Center for Electrochemical Energy StorageUnited States. Department of EnergyNational Energy Technology Laboratory (U.S.)Solid State Energy Conversion Alliance. Core Technology Program (DEFE0009435

Effects of postmilling time and temperature on the breadmaking quality and lipids of whole wheat flour

Master of ScienceDepartment of Grain Science and IndustryJon M. FaubionThis work investigated the relationship between flour age (days post-milling), storage condition (temperature), and the bread baking quality of whole wheat flour. A laboratory scale milling method was designed to mimic the particle size distribution of commercially milled whole wheat flours and the 100 g ‘pup’ loaf baking method was adapted for use with whole wheat doughs. Laboratory milled whole wheat flour (Karl 92) was subjected to a 21 day storage study at two storage temperatures (72 & -15 F) with quality (baking) and chemical (lipids) analyses conducted every three days. Parameters for quality analysis included: loaf weight, volume & specific volume, as well as slice area, cell number, wall thickness, cell diameter, elongation, and non-uniformity. Three lipid classes (glycolipids, phospholipids, and neutral lipids) were extracted and analyzed by TLC with quantification by computerized analysis of spot size and density. Results were analyzed by ANOVA. Analysis of the loaf quality data revealed no trends in volume or specific volume as a function of storage time or temperature, although values for some specific days were significantly different. Likewise, analysis of crumb characteristics revealed no consistent trends for either time or storage temperature. Again, values for some, but not all, parameters (area, brightness, wall thickness, cell diameter, and non-uniformity) were significantly different for specific days of the study. Analysis of lipids revealed no consistent trends for either time or storage temperature. However, values for some lipid classes (total glycolipids, free phospholipids, and total phospholipids) were significantly different for storage temperature, and values for total neutral lipids were significantly different for specific days of the study. Suggested future research opportunities include: using new crop wheat, increasing storage duration, performing WW flour lipid exchange studies, and using lipid profiling to identify and more closely track changes in individual lipid species

Toward the rational design of non-precious transition metal oxides for oxygen electrocatalysis

In this Review, we discuss the state-of-the-art understanding of non-precious transition metal oxides that catalyze the oxygen reduction and evolution reactions. Understanding and mastering the kinetics of oxygen electrocatalysis is instrumental to making use of photosynthesis, advancing solar fuels, fuel cells, electrolyzers, and metal–air batteries. We first present key insights, assumptions and limitations of well-known activity descriptors and reaction mechanisms in the past four decades. The turnover frequency of crystalline oxides as promising catalysts is also put into perspective with amorphous oxides and photosystem II. Particular attention is paid to electronic structure parameters that can potentially govern the adsorbate binding strength and thus provide simple rationales and design principles to predict new catalyst chemistries with enhanced activity. We share new perspective synthesizing mechanism and electronic descriptors developed from both molecular orbital and solid state band structure principles. We conclude with an outlook on the opportunities in future research within this rapidly developing field.National Science Foundation (U.S.) (DMR - 0819762)National Science Foundation (U.S.) (DGE-1122374

Oxygen Reduction at Carbon Supported Lanthanides:The Role of the B-site

The kinetics of the oxygen reduction reaction (ORR) at carbon supported transition metal oxides in alkaline solutions is systematically investigated as a function of the nature of the B-site. The study is focused on LaBO3 (B = Cr, Co, Fe, Mn and Ni) nanoparticles synthesized by an ionic liquid route, offering fine control over phase purity and composition. Activity towards the ORR was compared with commercial Pt/Etek catalyst. Detailed electrochemical analysis employing a rotating ring-disc electrode provides conclusive evidences that the carbon support plays an important contribution in the faradaic responses. Decoupling the contribution of the carbon support uncovers that the reactivity of LaMnO3 towards the 4e- ORR pathway is orders of magnitude higher than for the other lanthanides. We rationalise these observations in terms of changes in the redox state at the B-site close to the formal oxygen reduction potential

Redox Processes of Manganese Oxide in Catalyzing Oxygen Evolution and Reduction: An

Manganese oxides with rich redox chemistry have been widely used in (electro)catalysis in applications of energy and environmental consequence. While they are ubiquitous in catalyzing the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), redox processes occurring on the surface of manganese oxides are poorly understood. We report valence changes at OER- and ORR-relevant voltages of a layered manganese oxide film prepared by electrodeposition. X-ray absorption spectra were collected in situ in O[subscript 2]-saturated 0.1 M KOH using inverse partial fluorescence yield (IPFY) at the Mn L[subscript 3,2]-edges and partial fluorescence yield (PFY) at the O K-edge. Overall, we found reversible yet hysteretic Mn redox and qualitatively reproducible spectral changes by Mn L[subscript 3,2]IPFY XAS. Oxidation to a mixed Mn[superscript 3+/4+] valence preceded the oxygen evolution at 1.65 V vs RHE, while manganese reduced below Mn[superscript 3+] and contained tetrahedral Mn[superscript 2+] during oxygen reduction at 0.5 V vs RHE. Analysis of the pre-edge in O K-edge XAS provided the Mn-O hybridization, which was highest for Mn[superscript 3+](e[subscript g][superscript 1]). Our study demonstrates that combined in situ experiments at the metal L- and oxygen K-edges are indispensable to identify both the active valence during catalysis and the hybridization with oxygen adsorbates, critical to the rational design of active catalysts for oxygen electrocatalysis.National Science Foundation (U.S.) (Grant DGE-1122374

Reversibility of Ferri-/Ferrocyanide Redox during Operando Soft X-ray Spectroscopy

The ferri-/ferrocyanide redox couple is ubiquitous in many fields of physical chemistry. We studied its photochemical response to intense synchrotron radiation by in situ X-ray absorption spectroscopy (XAS). For photon flux densities equal to and above 2 × 1011 s–1 mm–2, precipitation of ferric (hydr)oxide from both ferricyanide and ferrocyanide solutions was clearly detectable, despite flowing fast enough to replace the solution in the flow cell every 0.4 s (flow rate 1.5 mL/min). During cyclic voltammetry, precipitation of ferric (hydr)oxide was promoted at reducing voltages and observed below 1011 s–1 mm–2. This was accompanied by inhibition of the ferri-/ferrocyanide redox, which we probed by time-resolved operando XAS. Our study highlights the importance of considering both electrochemical and spectroscopic conditions when designing in situ experiments

Reactivity of Perovskites with Water: Role of Hydroxylation in Wetting and Implications for Oxygen Electrocatalysis

Oxides are instrumental to applications such as catalysis, sensing, and wetting, where the reactivity with water can greatly influence their functionalities. We find that the coverage of hydroxyls (*OH) measured at fixed relative humidity trends with the electron-donor (basic) character of wetted perovskite oxide surfaces. Using ambient pressure X-ray photoelectron spectroscopy, we report that the affinity toward hydroxylation, coincident with strong adsorption energies calculated for dissociated water and hydroxyl groups, leads to strong H bonding that is favorable for wetting while detrimental to catalysis of the oxygen reduction reaction (ORR). Our findings provide novel insights into the coupling between wetting and catalytic activity and suggest that catalyst hydrophobicity should be considered in aqueous oxygen electrocatalysis.National Science Foundation (U.S.). Materials Research Science and Engineering Centers (Program) (Award DMR-0819762)National Science Foundation (U.S.). Graduate Research Fellowship (Grant DGE-1122374)National Science Foundation (U.S.) (Career Award (0952564

Mass-Production of Mesoporous MnCo2O4 Spinels with Manganese(IV)- and Cobalt(II)-Rich Surfaces for Superior Bifunctional Oxygen Electrocatalysis

A mesoporous MnCo2O4 electrode material is made for bifunctional oxygen electrocatalysis. The MnCo2O4 exhibits both Co3O4-like activity for oxygen evolution reaction (OER) and Mn2O3-like performance for oxygen reduction reaction (ORR). The potential difference between the ORR and OER of MnCo2O4 is as low as 0.83 V. By XANES and XPS investigation, the notable activity results from the preferred MnIVand CoII-rich surface. The electrode material can be obtained on large-scale with the precise chemical control of the components at relatively low temperature. The surface state engineering may open a new avenue to optimize the electrocatalysis performance of electrode materials. The prominent bifunctional activity shows that MnCo2O4 could be used in metal-air batteries and/or other energy devices.Peer reviewe