CuO-CeO2 catalysts synthesized in one-step: Characterization and PROX performance

PEM fuel cells seem to be the most affordable and commercially viable hydrogen-based cells, the biggest challenge being to obtain CO-free H-2 (<100 ppm) as the fuel. In this study, the use of CuO-CeO2 catalysts in preferential oxidation of CO to obtain CO-free H-2 (PROX reaction) was investigated. Ce1-xCuxO2 catalysts, with x (mol%) = 0, 0.01, 0.03, 0.05 and 0.10, were synthesized in one-step by the polymeric precursor method, to obtain a very fine dispersion and strong metal-support interaction, to favor active copper species and a preference for the PROX reaction. The results obtained from catalyzed reactions and characterization of the catalysts by XRD, Rietveld refinement, BET surface area, UV-Vis and TPR, suggest that this one-step synthesis method gives rise to catalysts with copper species selective for the PROX reaction, which reaches a maximum rate on Ce0.97Cu0.03O2 catalyst. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Photoemissions-Elektronenmikroskopie an Adsorbatsystemen

Die Photoemissions-Elektronenmikroskopie ist eine hervorragend geeignete Methode zur Untersuchung dynamischer Vorgänge auf realen polykristallinen Oberflächen im sub-μm Bereich. Bei der Anwendung auf Adsorbatsysteme lassen sich geringe Bedeckungsunterschiede, sowie Adsorbatstrukturen und -phasen unterscheiden. Die Methode erlaubt dabei ein breites Anwendungsspektrum über weite Temperaturbereiche und Systeme unterschiedlichster Bindungsenergie. Bei der Chemisorption von Sauerstoff auf polykristallinen Metallen wird unterschiedliches Aufwachsverhalten in den Helligkeitswerten im Mikroskopbild widergespiegelt. Bei Kupferproben zeigen Oberflächen mit unterschiedlicher kristalliner Richtung aufgrund der Symmetrie des fcc-Gitters ein ähnliches Verhalten. Das hexagonale Gitter des Titans zeigt dagegen große Unterschiede im Adsorptionsverhalten in Abhängigkeit der kristallinen Richtung. Diese Unterschiede konnten auf verschiedene Haftkoeffizienten und Oxidationsstufen der Metalle zurückgeführt werden. In einem Modell zur Photostromanalyse konnte beim Kupfer der Übergang von verschiedenen Überstrukturen bei wachsender Bedeckung gezeigt und die Übergänge ermittelt werden.. Auf den Titanoberflächen wurde so das Wachstum der Oxide TiO, TiO₂ und Ti₂O₃ unterschieden und die Übergänge des unterschiedlichen Wachstums ermittelt. Bei der thermischen Desorption der Schichten konnten unterschiedliche Haftkoeffizient auf einzelnen Kristalliten qualitativ gezeigt werden. Diese erstmalig eingesetzte Analysemethode weist Ähnlichkeiten zur Thermo-Desorptions-Spektroskopie (TDS) auf, zeigt jedoch ortsaufgelöst lokale Unterschiede auf polykristallinen Oberflächen. Bei thermisch gestützten Oberflächenreaktionen ließen sich die Reaktionskeime deutlich identifizieren und mit einer Grauwertanalyse konnte die Oxidation der karbidischen Lagen zu Kohlenmonoxid und die Metalloxidation unterschieden werden. Dabei konnte gezeigt werden, daß die Reaktionskeime nur an Plattengrenzen auftreten, nicht jedoch auf der Oberfläche. Durch die Aufrauhung der Plattengrenzen mit zunehmender Reaktionsdauer nimmt die Zahl der Reaktionskeime kontinuierlich zu, die laterale Ausdehnung der Einzelreaktionen bleibt aber konstant. Bei der Physisorption von Xenon auf Graphit wurde erstmals für die Photoemissionsmikroskopie die resonanten Anregung ausgenutzt. Die verschiedenen Phasen des Adsorbats können dabei deutlich unterschieden werden; bei niedrigen Temperaturen (40K) findet ein gleichmäßiges Wachstum auf der gesamten Oberfläche statt, bei höheren Temperaturen von 60-65K ist dagegen ein Inselwachstum in verschiedenen Phasen zu beobachten. Die zeitliche Entwicklung des Wachstums, die örtliche Lage der Phasen und die Phasenübergänge (gas, fest inkommensurabel, fest kommensurabel) konnten bestimmt werden. Bei der Desorption der Schichten konnten die einzelnen Phasen ebenfalls getrennt werden und das unterschiedliche Desorptionsverhalten sowie die Phasenübergänge selber verifiziert werden.

CH4, CO, and H2O spectroscopy for the Sentinel-5 Precursor mission: an assessment with the Total Carbon Column Observing Network measurements

The TROPOspheric Monitoring Instrument (TROPOMI) will be part of ESA's Sentinel-5 Precursor (S5P) satellite platform scheduled for launch in 2015. TROPOMI will monitor methane and carbon monoxide concentrations in the Earth's atmosphere by measuring spectra of back-scattered sunlight in the short-wave infrared (SWIR). S5P will be the first satellite mission to rely uniquely on the spectral window at 4190–4340 cm−1 (2.3 μm) to retrieve CH4 and CO. In this study, we investigated if the absorption features of the three relevant molecules CH4, CO, and H2O are adequately known. To this end, we retrieved total columns of CH4, CO, and H2O from absorption spectra measured by two ground-based Fourier transform spectrometers that are part of the Total Carbon Column Observing Network (TCCON). The retrieval results from the 4190–4340 cm−1 range at the TROPOMI resolution (0.45 cm−1) were then compared to the CH4 results obtained from the 6000 cm−1 region, and the CO results obtained from the 4190–4340 cm−1 region at the higher TCCON resolution (0.02 cm−1). For TROPOMI-like settings, we were able to reproduce the CH4 columns to an accuracy of 0.3% apart from a constant bias of 1%. The CO retrieval accuracy was, through interference, systematically influenced by the shortcomings of the CH4 and H2O spectroscopy. In contrast to CH4, the CO column error also varied significantly with atmospheric H2O content. Unaddressed, this would introduce seasonal and latitudinal biases to the CO columns retrieved from TROPOMI measurements. We therefore recommend further effort from the spectroscopic community to be directed at the H2O and CH4 spectroscopy in the 4190–4340 cm−1 region.

Cytochrome P450 2D18 in the mammalian brain: Recombinant expression, purification, and characterization of xenobiotic and endobiotic metabolism

The cytochromes P450 (P450) comprise a superfamily of hemoproteins that function in concert with NADPH-cytochrome P450 reductase (P450-reductase) to metabolize both endogenous and exogenous compounds. Many pharmacological agents undergo phase I metabolism by this P450 and P450-reductase monooxygenase system. Phase I metabolism ensures that these highly hydrophobic xenobiotics are made more hydrophilic, and hence easier to extrude from the body. While the majority of phase I metabolism occurs in the liver, metabolism in extrahepatic organ-systems like the intestine, kidney, and brain can have important roles in drug metabolism and/or efficacy. ^ While P450-mediated phase I metabolism has been well studied, investigators have only recently begun to elucidate what physiological roles P450 may have. One way to approach this question is to study P450s that are highly or specifically expressed in extrahepatic tissues. In this project I have studied the role of a recently cloned P450 family member, P450 2D18, that was previously shown to be expressed in the rat brain and kidney, but not in the liver. To this end, I have used the baculovirus expression system to over-express recombinant P450 2D18 and purified the functional enzyme using nickel and hydroxylapatite chromatography. SDS-PAGE analysis indicated that the enzyme was purified to electrophoretic homogeneity and Western analysis showed cross-reactivity with rabbit anti-human P450 2D6. Carbon monoxide difference spectra indicated that the purified protein contained no denatured P450 enzyme; this allowed for further characterization of the substrates and metabolites formed by P450 2D18-mediated metabolism. ^ Because P450 2D18 is expressed in brain, we characterized the activity toward several psychoactive drugs including the antidepressants imipramine and desipramine, and the anti-psychotic drugs chlorpromazine and haloperidol. P450 2D18 preferentially catalyzed the N-demethylation of imipramine, desipramine, and chlorpromazine. This is interesting given the fact that other P450 isoforms form multiple metabolites from such compounds. This limited metabolic profile might suggest that P450 2D18 has some unique function, or perhaps a role in endobiotic metabolism. ^ Further analysis of possible endogenous substrates for P450 2D18 led to the identification of dopamine and arachidonic acid as substrates. It was shown that P450 2D18 catalyzes the oxidation of dopamine to aminochrome, and that the enzyme binds dopamine with an apparent KS value of 678 μM, a value well within reported dopamine concentration in brain dopaminergic systems. Further, it was shown that P450 2D18 binds arachidonic acid with an apparent KS value of 148 μM, and catalyzes both the ω-hydroxylation and epoxygenation of arachidonic acid to metabolites that have been shown to have vasoactive properties in brain, kidney, and heart tissues. These data provide clues for endogenous roles of P450 within the brain, and possible involvement in the pathogenesis of Parkinson's disease. ^

Precious metals and volatiles in rocks of the Mid-Atlantic Ridge near 15°20'N

Distribution patterns of gold, platinum group metals (PGE), and volatile components are studied in the main rock types of the Mid-Atlantic Ridge lithosphere (ultrabasites, gabbro, and basalts) from the transform fracture zone at 15°20'N. It is ascertained that PGE content depends on the reduction degree of fluids, on rock types, and on their formation conditions. It is noted that concentrations of refractory elements (Os, Ir, Rh) decrease, while those of fusible elements (Pt, Pd, Au) increase with depth. The chondrite type of distribution is only noted in the ultrabasite rocks. Increase in water and CO2 contents and in oxidation degree of fluids occurs with transition from basalts to ultrabasites, as well as from normal magmatic systems to fluid-enriched anomalous systems.