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At least 361 records · Page 20

Reconstruction of Thiospinel to Active Sites and Spin Channels for Water Oxidation

Water electrolysis is a promising technique for carbon neutral hydrogen production. A great challenge remains at developing robust and low-cost anode catalysts. Many pre-catalysts are found to undergo surface reconstruction to give high intrinsic activity in the oxygen evolution reaction (OER). The reconstructed oxyhydroxides on the surface are active species and most of them outperform directly synthesized oxyhydroxides. The reason for the high intrinsic activity remains to be explored. Here, a study is reported to showcase the unique reconstruction behaviors of a pre-catalyst, thiospinel CoFe 2 S 4 , and its reconstruction chemistry for a high OER activity. The reconstruction of CoFe 2 S 4 gives a mixture with both Fe–S component and active oxyhydroxide (Co(Fe)O x H y ) because Co is more inclined to reconstruct as oxyhydroxide, while the Fe is more stable in Fe–S component in a major form of Fe 3 S 4 . The interface spin channel is demonstrated in the reconstructed CoFe 2 S 4 , which optimizes the energetics of OER steps on Co(Fe)O x H y species and facilitates the spin sensitive electron transfer to reduce the kinetic barrier of O–O coupling. The advantage is also demonstrated in a membrane electrode assembly (MEA) electrolyzer. Finally, this work introduces the feasibility of engineering the reconstruction chemistry of the precatalyst for high performance and durable MEA electrolyzers.

36 MATERIALS SCIENCE↗

Non-noble electrocatalysts for alkaline fuel cells

Carbons activated with macrocyclics have attracted increasing attention as alternative electrocatalysts for oxygen reduction. Initial activity of these catalysts is good, but performance declines rapidly. Pyrolyzing the macrocyclic on the carbon support leads to enhanced stability and the catalysts retain good activity. The approach described is designed to develop bulk doped catalysts with similar structures to pyrolyzed macrocyclic catalysts. The transition metal and coordinated ligands are dispersed throughout the bulk of the conductive carbon skeleton. Two approaches to realizing this concept are being pursued, both involving the doping of carbon precursors. In one approach, the precursor is a solid phase carbon-containing ion-exchange resin. The precursor is doped with a transition metal and/or nitrogen, and the resulting mixture is pyrolyzed. In the other approach, the precursor is a gas-phase hydrocarbon. This is introduced with a transition metal species and nitrogen species into a reactor and pyrolyzed. Several studies have been conducted to determine if there is a synergistic effect between the transition metal and nitrogen and the effect of different methods of introducing the metal-nitrogen (M-N) coordination on performance. One approach was to introduce the metal and nitrogen separately, for example, by sequentially doping FeCl3 and NH4OH into the resin. Catalysts were prepared from an undoped ion-exchange resin, a resin doped only with N, a resin doped only with Fe, and a resin doped with both Fe and N. Introduction of nitrogen alone has no beneficial effect on the performance of the catalysts. The introduction of the Fe alone significantly improves the performance in both the high and low current density regions. When both Fe and N are introduced, the performance at lower current densities (catalytic activity) is increased beyond that of the Fe-doped carbon, but the performance at higher current densities is similar to the carbon containing only Fe. Catalysts prepared from resins-Fe(bipy)3SO4 precursors have performance that is only slightly less then CoTMPP adsorbed and pyroloyzed on Vulcan XC-72. Their performance is much better than carbons which have had the N and Fe introduced separately.

Sarangapani, S.↗

Method of Separating Oxygen From Spacecraft Cabin Air to Enable Extravehicular Activities

Extravehicular activities (EVAs) require high-pressure, high-purity oxygen. Shuttle EVAs use oxygen that is stored and transported as a cryogenic fluid. EVAs on the International Space Station (ISS) presently use the Shuttle cryo O2, which is transported to the ISS using a transfer hose. The fluid is compressed to elevated pressures and stored as a high-pressure gas. With the retirement of the shuttle, NASA has been searching for ways to deliver oxygen to fill the highpressure oxygen tanks on the ISS. A method was developed using low-pressure oxygen generated onboard the ISS and released into ISS cabin air, filtering the oxygen from ISS cabin air using a pressure swing absorber to generate a low-pressure (high-purity) oxygen stream, compressing the oxygen with a mechanical compressor, and transferring the high-pressure, high-purity oxygen to ISS storage tanks. The pressure swing absorber (PSA) can be either a two-stage device, or a single-stage device, depending on the type of sorbent used. The key is to produce a stream with oxygen purity greater than 99.5 percent. The separator can be a PSA device, or a VPSA device (that uses both vacuum and pressure for the gas separation). The compressor is a multi-stage mechanical compressor. If the gas flow rates are on the order of 5 to 10 lb (.2.3 to 4.6 kg) per day, the compressor can be relatively small [3 ~16 ~16 in. (.8 ~41 ~41 cm)]. Any spacecraft system, or other remote location that has a supply of lowpressure oxygen, a method of separating oxygen from cabin air, and a method of compressing the enriched oxygen stream, has the possibility of having a regenerable supply of highpressure, high-purity oxygen that is compact, simple, and safe. If cabin air is modified so there is very little argon, the separator can be smaller, simpler, and use less power.

Graf, John C.↗

Fundamentals of SrCoO 3-δ Based Oxygen Deficient Perovskites as Cathodes for Solid Oxide Fuel Cells

The local structure and oxygen stoichiometry in oxide systems have a profound impact on oxygen electrocatalysis encountered in metal-air batteries and solid oxide fuel cells (SOFCs). However, this knowledge is often obtained under conditions different from the real working conditions of the material, resulting in misinterpretation and misunderstanding. This PhD dissertation aims to obtain the structure and oxygen-stoichiometry information of a class of perovskite oxides under their real working conditions in solid oxide fuel cells. Several perovskite oxides were selected for the study: Sr 0.9 Y 0.1 CoO 3-δ (SYC10), Sr 0.9 Y 0.3 CoO 3-δ (SYC30), SrCo 0.9 Nb 0.1 O 3-δ (SCN10) and SrCo 0.9 Ta0.1O 3-δ (SCT10). The local crystal structure and oxygen stoichiometry of these materials were systematically characterized with in-situ neutron diffraction (ND). The oxygen stoichiometry was also measured by thermogravimetric analysis (TGA) and iodometric titration methods. To establish the correlation among structure, oxygen stoichiometry and oxygen reduction reaction (ORR) activity, high temperature electrochemical impedance spectroscopy, oxygen permeation and single cell testing were also performed. In chapter 2, SYC10 is described to have a more symmetrical structure and $V_o^{··}$ distribution, and higher $V_o^{··}$ concentration than SYC30. Molecular orbital energy analysis based on the local structure of the ORR-active Co1-polyhedra indicates SYC30 has a higher Fermi level relative to O-2p energy level in the active Co1-polyhedra, and thus a higher motional enthalpy for $V_o^{··}$ migration. However, the ORR activity of Y-doped SrCoO 3-δ (SCO) are found uncompetitive with other popular catalysts. In chapter 3 and 4, systematic structural studies are presented for Nb and Ta-doped SCO, namely SCN10 and SCT10, respectively. The methodology of unrevealing the structure-activity relationships in chapter 2 is also found applicable to SYC10, SCN10 and SCT10 as presented in chapter 5. The electrochemical tests indicate that SCT10 is the best catalyst due to its excellent thermal and electrochemical stability. In chapter 6, SCT10 is evaluated in a real solid oxide fuel cell in the form of nanoscaled SCT10 layer coating on the commercial (La 0.6 Sr 0.4 ) 0.95 Co 0.2 Fe 0.8 O 3-δ (LSCF). The bilayer structured cathode shows excellent properties of coarsening-resistant, Sr-segregation-free and high ORR-activity.

Yang, Tianrang↗

Mixed conductive composites for ‘Low-Temperature’ thermo-chemical CO 2 splitting and syngas generation

An effective strategy to design platinum group metal (PGM) free redox catalysts for “low temperature” CO 2 splitting followed with methane partial oxidation was proposed and validated. Composites of mixed ionic-electronic conductive (MIEC) oxides were found to be highly effective at relatively low temperatures (600–750 °C). Specifically, perovskite structured LaNi 0.35 Fe 0.65 O 3 and rock salt structured Ce 0.85 Gd 0.1 Cu 0.05 O 2–δ , as two compatible yet structurally distinct MIEC oxides, were integrated into composite redox catalyst particles. Resulting from the synergistic effect of the two MIEC phases, 90% CO 2 to CO conversion was demonstrated at 750 °C. Up to 90% methane conversion with 96% CO selectivity was also achieved in the methane POx step. The redox catalysts were characterized in detail to illustrate the underlying mechanisms for the synergistic effects. Electrical conductivity relaxation (ECR) measurements indicated significantly lowered activation energy for lattice oxygen (O 2– ) migration (0.43 eV). The enhanced oxygen migration in turn led to reversible exsolution of active transition metal nanoparticles (Ni–Fe alloy) from the mixed oxide, serving as active sites for methane activation while further enhancing lattice oxygen exchange, as confirmed by in situ X-ray diffraction and transmission electron microscopy. In conclusion, the composite redox catalysts demonstrate superior redox activity, coke resistance, and long term redox stability, making them potentially suitable for CO 2 utilization and methane partial oxidation under a hybrid redox process scheme.

03 NATURAL GAS↗

Determination of oxygen in silicon and carbide by activation with 27.2 meV alpha particles

The Si sample was polished on one side, and on the other side Ni was applied chemically and soldered with Pb to a water cooled Cu substrate. Optical quartz standard was fixed from the other side. Si carbide samples were soldered to a substrated with In. The prepared samples were irradiated in a cyclotron with a 27.2 MeV alpha particle beam. The layers were removed from the Si and Si carbide samples by grinding and the positron activity of F-18(t sub 1/2 110 min) was measured by using a gamma, gamma coincidence spectrometer with two NaI(TI) crystals. For analysis of Si carbide, the activity decay curve of the samples was recorded to find the contribution of the positron activity of Cu-65(t sub 1/2 12.9 hr) which formed from Ni impurity on irradiation.

Dolgolenko, A. P.↗

Enhanced Activity in Layered Metal-Oxide-Based Oxygen Evolution Catalysts by Layer-by-Layer Modulation of Metal-Ion Identity

Few-layered potassium nickel and cobalt oxides show drastic differences in catalytic activity based on metal ion preorganization. Uniform compositions [(CoO 2 /K) 6 or (NiO 2 /K) 6 ] show limited activity, while homogeneously mixed-metal cobalt/nickel oxides [(Co n Ni (1–n) O 2 /K) 6 ] display moderate improvement. However, a layer-by-layer arrangement of alternating cobalt and nickel oxide sheets [e.g., (CoO 2 /K/NiO 2 /K)] provides superior catalytic performance, reducing the oxygen evolution overpotential by ∼200–400 mV. Density functional theory simulations provide an illustration of the electronic properties (density of states and localization of orbitals) that promote catalysis in the layer-segregated materials over those of homogeneous composition. This study reveals that atomic preorganization of metal ions within layered catalysts plays a more crucial role than the overall metal composition in enhancing catalytic efficiency for oxygen evolution.

catalysts↗

Plasma lactic dehydrogenase activities in men during bed rest with exercise training

Peak oxygen uptake and the activity of lactic dehydrogenase (LDH-T) and its five isoenzymes were measured by spectrophotometer in seven men before, during, and after bed rest and exercise training. Exercise training consisted of isometric leg exercises of 250 kcal/hr for a period of one hour per day. It is found that LDH-T was reduced by 0.05 percent in all three regimens by day 10 of bed rest, and that the decrease occurred at different rates. The earliest reduction in LDH-T activity in the no-exercise regimen was associated with a decrease in peak oxygen uptake of 12.3 percent. It is concluded that isometric (aerobic) muscular strength training appear to maintain skeletal muscle integrity better during bed rest than isotonic exercise training. Reduced hydrostatic pressure during bed rest, however, ultimately counteracts the effects of both moderate isometric and isotonic exercise training, and may result in decreased LDH-T activity.

Greenleaf, J. E.↗

Bifunctional catalytic electrode

The present invention relates to an oxygen electrode for a unitized regenerative hydrogen-oxygen fuel cell and the unitized regenerative fuel cell having the oxygen electrode. The oxygen electrode contains components electrocatalytically active for the evolution of oxygen from water and the reduction of oxygen to water, and has a structure that supports the flow of both water and gases between the catalytically active surface and a flow field or electrode chamber for bulk flow of the fluids. The electrode has an electrocatalyst layer and a diffusion backing layer interspersed with hydrophilic and hydrophobic regions. The diffusion backing layer consists of a metal core having gas diffusion structures bonded to the metal core.

Cisar, Alan↗

Design of a lunar oxygen production plant

To achieve permanent human presence and activity on the moon, oxygen is required for both life support and propulsion. Lunar oxygen production using resources existing on the moon will reduce or eliminate the need to transport liquid oxygen from earth. In addition, the co-products of oxygen production will provide metals, structural ceramics, and other volatile compounds. This will enable development of even greater self-sufficiency as the lunar outpost evolves. Ilmenite is the most abundant metal-oxide mineral in the lunar regolith. A process involving the reaction of ilmenite with hydrogen at 1000 C to produce water, followed by the electrolysis of this water to provide oxygen and recycle the hydrogen has been explored. The objective of this 1990 Summer Faculty Project was to design a lunar oxygen-production plant to provide 5 metric tons of liquid oxygen per year from lunar soil. The results of this study describe the size and mass of the equipment, the power needs, feedstock quantity and the engineering details of the plant.

Radhakrishnan, Ramalingam↗

Oxygen as a factor in eukaryote evolution - Some effects of low levels of oxygen on Saccharomyces cerevisiae

A comparative study of the effects of varying levels of oxygen on some of the metabolic functions of the primitive eukaryote, Saccharomyces cerevisiae, has shown that these cells are responsive to very low levels of oxygen: the level of palmitoyl-Co A desaturase was greatly enhanced by only 0.03 vol % oxygen. Similarly, an acetyl-CoA synthetase associated predominantly with anaerobic growth was stimulated by as little as 0.1% oxygen, while an isoenzyme correlated with aerobic growth was maximally active at much higher oxygen levels (greater than 1%). Closely following this latter pattern were three mitochondrial enzymes that attained maximal activity only under atmospheric levels of oxygen.

Jahnke, L.↗