Study of surface oxidation of rare-earth-metals by photoelectron-spectroscopy

Surface oxidation of La, Ce, Sm and Tb metals has been investigated by He(II) ultraviolet photoelectron spectroscopy (u.p.s.) and X-ray photoelectron spectroscopy (X.p.s.). Oxidation of La gives rise to La2O3 on the surface. While Ce2O3 appears to be the stable oxide on the surface, we find evidence for formation of CeO2 at high oxygen exposure. Valence band of Sm clearly shows the presence of both divalent and trivalent states due to interconfigurational fluctuation. Exposure of Sm to oxygen first depletes the divalent Sm at the surface. While Sm2O3 is the stable oxide on the surface of Sm, Tb2O3 is the stable oxide on the surface of Tb (and not any of the higher oxides).

Dioxomolybdenum reagents in organic synthesis: utility of redox capability to design reduction and oxidation

The usefulness of dioxomolybdenum reagents in oxo-transfer reactions have been reviewed. The redox ability of dioxomolybdenum reagent has been utilized in designing several synthetic methods, which are useful in organic synthesis. Several reactions such as oxidation of alcohols, sulfides, amines, azides olefins etc are accomplished by using dioxomolybdenum reagents. Similarly, it is also demonstrated that dioxomolybdenum complex is useful in performing reduction of aldehydes, ketones, esters, azides etc. A fine tuning of reaction conditions provides suitable conditions to perform either oxidation or reduction by using catalytic amount of reagents. The oxidation reactions are further simplified by employing the polymer supported molybdenum reagents.

Evidences for ambient oxidation of indium nitride quantum dots

Investigations were carried out on the ambient condition oxidation of self-assembled, fairly uniform indium nitride (InN) quantum dots (QDs) fabricated on p-Si substrates. Incorporation of oxygen in to the outer shell of the QDs was confirmed by the results of transmission electron microscopy (TEM), X-ray photoemission spectroscopy (XPS). As a consequence, a weak emission at high energy (similar to 1.03?eV) along with a free excitonic emission (0.8?eV) was observed in the photoluminescence spectrum. The present results confirm the incorporation of oxygen into the lattice of the outer shell of InN QDs, affecting their emission properties. (C) 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

C-H functionalization of tertiary amines by cross dehydrogenative coupling reactions: solvent-free synthesis of alpha-aminonitriles and beta-nitroamines under aerobic condition

A solvent-free synthesis of alpha-aminonitriles and beta-nitroamines by oxidative cross-dehydrogenative coupling under aerobic condition is reported. A catalytic amount of molybdenum(VI) acetylacetonoate was found to catalyze cyanation of tertiary amines to form alpha-aminonitriles, whereas vanadium pentoxide was found to promote aza-Henry reaction to furnish beta-nitroamines. Both of these environmentally benign reactions are performed in the absence of solvents using molecular oxygen as an oxidant.

Kinetics of carbon monoxide oxidation with Sn(0.95)M(0.05)O(2-delta) (M = Cu, Fe, Mn, Co) catalysts

Base metal substituted Sn(0.95)M(0.05)O(2-delta) (M = Cu, Fe, Mn, Co) catalysts were synthesized by the solution combustion method and characterized by XRD, XPS, TEM and BET surface area analysis. The catalytic activities of these materials were investigated by performing CO oxidation. The rates and the apparent activation energies of the reaction for CO oxidation were determined for each catalyst. All the substituted catalysts showed high rates and lower activation energies for the oxidation of CO as compared to unsubstituted SnO(2). The rate was found to be much higher over copper substituted SnO(2) as compared to other studied catalysts. 100% CO conversion was obtained below 225 degrees C over this catalyst. A bifunctional reaction mechanism was developed that accounts for CO adsorption on base metal and support ions and O(2) dissociation on the oxide ion vacancy. The kinetic parameters were determined by fitting the model to the experimental data. The high rates of the CO oxidation reactions at low temperatures were rationalized by the high dissociative chemisorption of adsorbed O(2) over these catalysts.

Spatiotemporal chaos in a model for CO oxidation on Pt(110)

We present numerical studies of a model for CO oxidation on the surface of Pt(110) proposed in Ref. 1. The model shows several interesting regimes, some of which exhibit spatiotemporal chaos. The time series of the CO concentration at a given point consists of a sequence of pulses. We concentrate on interpulse intervals theta and show that their distribution P(theta) approaches a delta function continuously as the system goes from a state M, with meandering spirals, to a state S, with spatially frozen spiral cores. This should be verifiable experimentally.

Performance evaluation of nonthermal plasma reactors for NO oxidation in diesel engine exhaust gas treatment

The discharge plasma-chemical hybrid process for NO/sub x/ removal from the due gas emissions is an extremely effective and economical approach in comparison with the conventional selective catalytic reduction system. In this paper we bring out a relative comparison of several discharge plasma reactors from the point of NO removal efficiency. The reactors were either energized by AC or by repetitive pulses. Ferroelectric pellets were used to study the effect of pellet assisted discharges on gas cleaning. Diesel engine exhaust, at different loads, is used to approximately simulate the due gas composition. Investigations were carried out at room temperature with respect to the variation of reaction products against the discharge power. Main emphasis is laid on the oxidation of NO to NO/sub 2/, without reducing NOx concentration (i.e., minimum reaction byproducts), with least power consumption. The produced NO/sub 2/ will be totally converted to N/sub 2/ and Na/sub 2/SO/sub 4/ using Na/sub 2/SO/sub 3/. The AC packed bed reactor and pelletless pulsed corona reactor showed better performance, with minimum reaction products for a given power, when the NO concentration was low (/spl sim/100 ppm). At high engine loads (NO>300 ppm) there was not much decrease in NO/sub x/ reduction and more or less all the reactors performed equally. The paper discusses these observations in detail.

Molybdenum trioxide catalyzed oxidative cross-dehydrogenative coupling of benzylic sp(3) C-H bonds: synthesis of alpha-aminophosphonates under aerobic conditions

Molybdenum trioxide (MoO3) catalyzed efficient oxidative cross-dehydrogenative-coupling (CDC) method for C-H functionalization of N-aryl tetrahydroisoquinolines has been explored. This user-friendly method of synthesizing alpha-aminophosphonates employs 1.1 equiv of dialkyl-H-phosphonate under aerobic condition. Formation of new C-P bonds from unfunctionalized starting materials under environmentally benign conditions provides an excellent avenue for the synthesis of biologically active alpha-aminophosphonates. (C) 2012 Elsevier Ltd. All rights reserved.

Lewis Base Catalysis by Thiourea: N-Bromosuccinimide-Mediated Oxidation of Alcohols

In recent times, (thio)urea derivatives have become synonymous with hydrogen bonding owing to their extensive applicability as small molecule organocatalysts. In this paper, another activation mode by thiourea derivatives, namely via Lewis base catalysis, is disclosed for the NBS-mediated oxidation of alcohols. The mild reaction conditions employed here is suitable for chemoselective oxidation of secondary alcohol in the presence of primary alcohol.

A non-metal catalysed oxidation of primary azides to nitriles at ambient temperature

A novel non-metal catalyzed oxidation of organic azides to nitriles under solvent-free conditions is presented employing catalytic amounts of KI, and DABCO in aq. TBHP at room temperature. This nonmetal catalyzed oxidation of azides provides good selectivity as double and triple bonds were not oxidized under the present reaction conditions.

In praise of H2O2, the versatile ROS, and its vanadium complexes

Hydrogenperoxide (H2O2) is generated in mitochondria in aerobic cells as a minor product of electron transport, is inhibited selectively by phenolic acids (in animals) or salicylhydroxamate (in plants) and is regulated by hormones and environmental conditions. Failure to detect this activity is due to presence of H2O2-consuming reactions or inhibitors present in the reaction mixture. H2O2 has a role in metabolic regulation and signal transduction reactions. A number of enzymes and cellular activities are modified, mostly by oxidizing the protein-thiol groups, on adding H2O2 in mM concentrations. On complexing with vanadate, also occurring in traces, H2O2 forms diperoxovanadate (DPV), stable at physiological pH and resistant to degradation by catalase. DPV was found to substitute for H2O2 at concentrations orders of magnitude lower, and in presence of catalase, as a substrate for user reaction, horseradish peroxidase (HRP), and in inactivating glyceraldehyde-3-phosphate dehydrogenase. superoxide dismutase (SOD)-sensitive oxidation of NADH was found to operate as peroxovanadate cycle using traces of DPV and decameric vanadate (V-10) and reduces O-2 to peroxide (DPV in presence of free vanadate). This offers a model for respiratory burst. Diperoxovanadate reproduces several actions of H2O2 at low concentrations: enhances protein tyrosine phosphorylation, activates phospholipase D, produces smooth muscle contraction, and accelerates stress induced premature senescence (SIPS) and rounding in fibroblasts. Peroxovanadates can be useful tools in the studies on H2O2 in cellular activities and regulation.