An investigation of alternative catalytic approaches for the direct synthesis of hydrogen peroxide from hydrogen and oxygen

Catalytic systems for the direct production of hydrogen peroxide from hydrogen and oxygen are investigated, and the factors which make a successful process identified. The use of low metal loadings, an organic co-solvent (such as ethanol) and reduced palladium as the catalytic metal all lead to good activity and selectivity. (C) 2002 Elsevier Science B.V. All rights reserved.

Origin of Low CO2 Selectivity on Platinum in the Direct Ethanol Fuel Cell

Calculated answer: First-principles calculations have been applied to calculate the energy barrier for the key step in CO formation on a Pt surface (see picture; Pt blue, Pt atoms on step edge yellow) to understand the low CO2 selectivity in the direct ethanol fuel cell. The presence of surface oxidant species such as O (brown bar) and OH (red bar) led to an increase of the energy barrier and thus an inhibition of the key step. © 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Acetaldehyde Production in the Direct Ethanol Fuel Cell: Mechanistic Elucidation by Density Functional Theory

This study employs density functional theory (DFT) calculations to examine the mechanism by which acetaldehyde is formed on platinum in a typical direct ethanol fuel cell (DEFC). A pathway is found involving the formation of a strongly hydrogen-bonded complex between adsorbed ethanol and the surface hydroxyl (OH) species, followed by the facile alpha-dehydrogenation of ethanol, with spontaneous weakening of the hydrogen bond in favor of adsorbed acetaldehyde and water. This mechanism is found to be comparably viable on both the close-packed surface and the monatomic steps. Comparison of further reactions on these two sites strongly indicates that the steps act as net removers of acetaldehyde from the product stream, while the flat surface acts as a net producer.

Evidence for the direct binding of phosphorylated p53 to sites of DNA breaks in vivo

Despite a clear link between ataxia-telangiectasia mutated (ATM)-dependent phosphorylation of p53 and cell cycle checkpoint control, the intracellular biology and subcellular localization of p53 phosphoforms during the initial sensing of DNA damage is poorly understood. Using GO-G, confluent primary human diploid fibroblast cultures, we show that endogenous p53, phosphorylated at Ser(15) (p53(Ser15)), accumulates as discrete, dose-dependent and chromatin-bound foci within 30 minutes following induction of DNA breaks or DNA base damage. This biologicafly distinct subpool of p53(Ser15) is ATM dependent and resistant to 26S-proteasomal degradation. p53(Ser15) colocalizes and coimmunoprecipitates with gamma-H2AX with kinetics similar to that of biochemical DNA double-strand break (DNA-dsb) rejoining. Subnuclear micro-beam irradiation studies confirm p53 S,,15 is recruited to sites of DNA damage containing gamma-H2AX, ATM(Ser1981), and DNA-PKcs(Thr2609) in vivo. Furthermore, studies using isogenic human and murine cells, which express Ser(15) or Ser(18) phosphomutant proteins, respectively, show defective nuclear foci formation, decreased induction of p21(WAF) decreased gamma-H2AX association, and altered DNA-dsb kinetics following DNA damage. Our results suggest a unique biology for this p53 phosphoform in the initial steps of DNA damage signaling and implicates ATM-p53 chromatin-based interactions as mediators of cell cycle checkpoint control and DNA repair to prevent carcinogenesis. (Cancer Res 2005; 65(23): 10810-21).

The meaning and function of the middens on Monte Ingino and Monte Ansciano119-0

Malone, C.A.T. and S.K.F. Stoddart, in, C. Malone and S. Stoddart, Editors. 1994, Cambridge University Press: Cambridge. p. 119-127.

PtRu/Ti anodes with varying Pt:Ru ratio prepared by electrodeposition for the direct methanol fuel cell

PtRu/Ti anodes with varying Pt : Ru ratio were prepared by electrodeposition of a thin PtRu catalyst layer onto Ti mesh for a direct methanol fuel cell (DMFC). The morphology and structure of the catalyst layers were analyzed by SEM, EDX and XRD. The catalyst coating layer shows an alloy character. The relative activities of the PtRu/Ti electrodes were assessed and compared in half cell and single DMFC experiments. The results show that these electrodes are very active for the methanol oxidation and that the optimum Ru surface coverage was ca. 9 at.% for DMFC operating at 20°C and 11 at.% at 60°C. The PtRu/Ti anode shows a performance comparable to that of the conventional carbon-based anode in a DMFC operating with 0.25 M or 0.5 M methanol solution and atmosphere oxygen gas at 90°C. © the Owner Societies 2006.

Ti mesh anodes prepared by electrochemical deposition for the direct methanol fuel cell

An anode structure based on Ti mesh has been developed for the direct methanol fuel cell (DMFC). This new anode was prepared by electrochemical deposition of a ~ 3 µ m PtRu catalyst layer on ~ 50 µ m Ti mesh. It has a thinner structure compared to that of a porous carbon-based conventional anode. The Ti mesh anode shows a performance comparable to, and exceeding that, of the conventional anode in a DMFC operating with 0.25 or 0.5 M methanol solution and atmosphere oxygen at 90 C. However, it shows a lower performance of the cell when higher concentrations of methanol was employed. This may be attributed to its thin and open structure, which could facilitate the transport of methanol from the flow field to the anode catalyst layer and carbon dioxide in the opposite direction. © 2006 International Association for Hydrogen Energy.

Critical role of water in the direct oxidation of CO and hydrocarbons in diesel exhaust after treatment catalysis

CO and C3H6 oxidation have been carried out in the absence and presence of water over a Pd/Al2O3catalyst. It is clear that water promotes CO and, as a consequence, C3H6oxidation takes place at muchlower temperatures compared with the dry feed. The significant increase in the catalyst’s activity withrespect to CO oxidation is not simply associated with changes in surface concentration as a result ofcompetitive adsorption effects. Utilising18O2as the reactant allows the pathways whereby the oxidationdue to gaseous dioxygen and where the water activates the CO and C3H6to be distinguished. In thepresence of water, the predominant pathway is via water activation with C16O2and C16O18O being themajor species formed and oxidation with dioxygen plays a secondary role. The importance of wateractivation is further supported by the significant decrease in its effect when using D2O versus H2O.