Catalysts for electrochemical generation of oxygen

Several aspects of the electrolytic evolution of oxygen for use in life support systems are analyzed including kinetic studies of various metal and nonmetal electrode materials, the formation of underpotential films on electrodes, and electrode surface morphology and the use of single crystal metals. In order to investigate the role of surface morphology to electrochemical reactions, a low energy electron diffraction and an Auger electron spectrometer are combined with an electrochemical thin-layer cell allowing initial characterization of the surface, reaction run, and then a comparative surface analysis

Catalysts for electrochemical generation of oxygen

Single crystal surfaces of platinum and gold and transition metal oxides of the spinel type were studied to find more effective catalysts for the electrolytic evolution of oxygen and to understand the mechanism and kinetics for the electrocatalysis in relation to the surface electronic and lattice properties of the catalyst. The single crystal studies involve the use of low energy electron diffraction (LEED) and Auger electron spectroscopy as complementary tools to the electrochemical measurements. Modifications to the transfer system and to the thin-layer electrochemical cell used to facilitate the transfer between the ultrahigh vacuum environment of the electron surface physics equipment and the electrochemical environment with a minimal possibility of changes in the surface structure, are described. The electrosorption underpotential deposition of Pb onto the Au(111), (100) and (110) single crystal surfaces with the thin-layer cell-LEED-Auger system is discussed as well as the synthesis of spinels for oxygen evolution studies

Catalysts for ultrahigh current density oxygen cathodes for space fuel cell applications

The objective was to identify promising electrocatalyst/support systems for oxygen cathodes capable of operating at ultrahigh current densities in alkaline fuel cells. Such cells will require operation at relatively high temperatures and O2 pressures. A number of materials were prepared, including Pb-Ru and Pb-Ir pyrochlores, RuO2 and Pt-doped RuO2, lithiated NiO and La-Ni perovskites. Several of these materials were prepared using techniques that had not been previously used to prepare them. Particularly interesting was the use of the alkaline solution technique to prepare Pt-doped and Pb-Ru pyrochlores in high area form. Also interesting was the use of the fusion (melt) method for preparing the Pb-Ru pyrochlore. Several of the materials were also deposited with platinum. Well-crystallized Pb2Ru2O(7-y) was used to fabricate very high performance O2 cathodes with good stability in room temperature KOH. This material was also found to be stable over a useful potential range at approx. 140 C in concentrated KOH. For some of the samples, fabrication of the gas-fed electrodes could not be fully optimized during this project period. Future work may be directed at this problem. Pyrochlores that were not well-crystallized were found to be unstable in alkaline solution. Very good O2 reduction performance and stability were observed with Pb2RuO(7-y) in a carbon-based gas-fed electrode with an anion-conducting membrane placed on the electrolyte side of the electrode. The performance came within a factor of about two of that observed without carbon. High area platinum and gold supported on several conductive metal oxide supports were examined. Only small improvements in O2 reduction performance at room temperature were observed for Pb2Ru2O(7-y) as a support because of the high intrinsic activity of the pyrochlore. In contrast, a large improvement was observed for Li-doped NiO as a support for Pt. Very poor performance was observed for Au deposited on Li-NiO at approx. 150 C. Nearly reversible behavior was observed for the O2/OH(-) couple for Li-doped NiO at approx. 200 C. The temperature dependence for the O2 reduction was examined

What does the Federal Reserve’s economic value model tell us about interest rate risk at U.S. community banks?

The savings and loan crisis of the 1980s revealed the vulnerability of some depository institutions to changes in interest rates. Since that episode, U.S. bank supervisors have placed more emphasis on monitoring the interest rate risk of commercial banks. One outcome developed by economists at the Federal Reserve Board of Governors was a duration-based Economic Value Model (EVM) designed to estimate the interest rate sensitivity of banks. ; We test whether measures derived from the Fed’s EVM are correlated with the interest rate sensitivity of U.S. community banks. The answer to this question is important because bank supervisors rely on EVM measures for monitoring and scoping bank-level interest rate sensitivity. ; We find that the Federal Reserve’s EVM is indeed correlated with banks’ interest rate sensitivity and conclude that supervisors can rely on this tool to help assess a bank’s interest rate risk. Our results are consistent with prior research that finds the average interest rate risk at banks to be modest, though we do not consider the potential interaction between interest rate risk and other risk factors.Community banks ; Risk management ; Interest rates

What does the Federal Reserve's economic value model tell us about interest rate risk at U.S. community banks?

The savings and loan crisis of the 1980s revealed the vulnerability of some depository institutions to changes in interest rates. Since that episode, U.S. bank supervisors have placed more emphasis on monitoring the interest rate risk of commercial banks. Economists at the Board of Governors of the Federal Reserve System developed a duration-based economic value model (EVM) designed to estimate the interest rate sensitivity of banks. The authors test whether measures derived from the Fed’s EVM are correlated with the interest rate sensitivity of U.S. community banks. The answer to this question is important because bank supervisors rely on EVM measures for monitoring and risk-scoping bank-level interest rate sensitivity. The authors find that the Federal Reserve’s EVM is indeed correlated with banks’ interest rate sensitivity and conclude that supervisors can rely on this tool to help assess a bank’s interest rate risk. These results are consistent with prior research that finds the average interest rate risk at banks to be modest, though the potential interaction between interest rate risk and other risk factors is not considered here.Risk management ; Interest rates ; Banks and banking

Electrochemical generation of oxygen. 1: The effects of anions and cations on hydrogen chemisorption and anodic oxide film formation on platinum electrode. 2: The effects of anions and cations on oxygen generation on platinum electrode

The effects were studied of anions and cations on hydrogen chemisorption and anodic oxide film formation on Pt by linear sweep voltammetry, and on oxygen generation on Pt by potentiostatic overpotential measurement. The hydrogen chemisorption and anodic oxide film formation regions are greatly influenced by anion adsorption. In acids, the strongly bound hydrogen occurs at more cathodic potential when chloride and sulfate are present. Sulfate affects the initial phase of oxide film formation by produced fine structure while chloride retards the oxide-film formation. In alkaline solutions, both strongly and weakly bound hydrogen are influenced by iodide, cyanide, and barium and calcium cations. These ions also influence the oxide film formation. Factors considered to explain these effects are discussed. The Tafel slope for oxygen generation was found to be independent on the oxide thickness and the presence of cations or anions. The catalytic activity indicated by the exchange current density was observed decreasing with increasing oxide layer thickness, only a minor dependence on the addition of certain cations and anions was found

Electrochemical Studies of Redox Systems for Energy Storage

Particular attention was paid to the Cr(II)/Cr(III) redox couple in aqueous solutions in the presence of Cl(-) ions. The aim of this research has been to unravel the electrode kinetics of this redox couple and the effect of Cl(1) and electrode substrate. Gold and silver were studied as electrodes and the results show distinctive differences; this is probably due to the role Cl(-) ion may play as a mediator in the reaction and the difference in state of electrical charge on these two metals (difference in the potential of zero charge, pzc). The competition of hydrogen evolution with CrCl3 reduction on these surfaces was studied by means of the rotating ring disk electrode (RRDE). The ring downstream measures the flux of chromous ions from the disk and therefore separation of both Cr(III) and H2 generation can be achieved by analyzing ring and disk currents. The conditions for the quantitative detection of Cr(2+) at the ring electrode were established. Underpotential deposition of Pb on Ag and its effect on the electrokinetics of Cr(II)/Cr(III) reaction was studied

Alternator and voltage regulator-exciter for a Brayton cycle space power system. Volume 2 - Unbalanced electromagnetic forces

Unbalanced electromagnetic forces in Brayton cycle turboalternator for space power syste

The (2k-1)-connected multigraphs with at most k-1 disjoint cycles

In 1963, Corr\'adi and Hajnal proved that for all $k \ge 1$ and $n \ge 3k$, every (simple) graph on n vertices with minimum degree at least 2k contains k disjoint cycles. The same year, Dirac described the 3-connected multigraphs not containing two disjoint cycles and asked the more general question: Which (2k-1)-connected multigraphs do not contain k disjoint cycles? Recently, the authors characterized the simple graphs G with minimum degree $\delta(G) \ge 2k-1$ that do not contain k disjoint cycles. We use this result to answer Dirac's question in full.Comment: 7 pages, 2 figures. To appear in Combinatoric