Direct oxidation of amines to nitriles in the presence of ruthenium-terpyridyl complex immobilized on ILs/SILP

The immobilization of a ruthenium complex (Ru2Cl4(az-tpy)2) within a range of supported ionic liquids ([C4C1im]Cl, [C4C1im][NTf2], [C6C1im]Cl, [C4C1pyrr]Br, [C4C1im]Br, [C4C1pyrr]Cl) dispersed silica (SILP) operates as an efficient heterogeneous catalyst in oxidation of long chain linear primary amines to corresponding nitriles. This reaction follows a “green” route using a cheap and easy to handles oxidant (oxygen or air). The conversion was found to be strongly influenced by the alkyl chain length of the amine substrate and the choice of oxidant. No condensation reaction was observed between the starting amines and the selectivity to nitrile is 100%. Moving from a composition of 20 atm N2/5 atm O2 to 5 atm N2/20 atm O2 led to enhancements in the conversion (n-alkylamines) and selectivity (benzonitrile) which have been correlated with an increase of the solubilized oxygen. This was further supported by using different inert gas (nitrogen, helium, argon)/oxygen mixtures indicating that the O2 solubility in the SILP system, has an important effect on conversions and TON in this reaction using SILP catalysts. Experiments performed in the presence of CO2 led to a different behaviour due to the formation of amine-CO2 adducts. The application of the Weisz–Prater criterion confirmed the absence of any diffusional constraints.

Efficient and selective hydrogen peroxide-mediated oxidation of sulfides in batch and segmented and continuous flow using a peroxometalate-based polymer immobilised ionic liquid phase catalyst

The peroxometalate-based polymer immobilized ionic liquid phase catalyst [PO4{WO(O-2)(2)}(4)]@PIILP has been prepared by anion exchange of ring opening metathesis-derived pyrrolidinium-decorated norbornene/ cyclooctene copolymer and shown to be a remarkably efficient system for the selective oxidation of sulfides under mild conditions. A cartridge packed with a mixture of [PO4{WO(O-2)(2)}(4)]@PIILP and silica operated as a segmented or continuous flow process and gave good conversions and high selectivity for either sulfoxide (92% in methanol at 96% conversion for a residence time of 4 min) or sulfone (96% in acetonitrile at 96% conversion for a residence time of 15 min). The immobilized catalyst remained active for 8 h under continuous flow operation with a stable activity/selectivity profile that allowed 6.5 g of reactant to be processed (TON = 46 428) while a single catalyst cartridge could be used for the consecutive oxidation of multiple substrates giving activity-selectivity profiles that matched those obtained with fresh catalyst.

Oxidation-induced Cu coating on steel surface

Copper is accumulated in recycled steels and is difficult to be removed during steelmaking processes when steel scrap is used as steel sources. Meanwhile, copper characteristic properties are of importance both to human beings and to animals and plants. In this paper, integrated copper coating was observed on the surface of copper-containing steels when the steels were heated at around 1150°C. However, the copper was separately scattered after heating at 1000°C. The forming mechanisms of copper coating will be discussed in detail. By choosing proper descaling reagent, self-generated oxidation-induced copper coating appeared on the steel surface. The method proposed in this work is environmentally friendly for nontoxic chemicals being used. In addition, this provides a new concept for producing protective composite by oxidizing from the substrate directly and there is no binding problem.

Oxidation-induced Cu coating on steel surface

Copper is accumulated in recycled steels and is difficult to be removed during steelmaking processes when steel scrap is used as steel sources. Meanwhile, copper characteristics are of importance both to human beings and to animals and plants. In this paper, integrated copper coating was observed on the surface of copper-containing steels when the steels were heated at around 1150°C. However, the copper was separately scattered in and under the surface rust after heating at 1000°C. The forming mechanisms of copper coating are discussed in detail. By choosing a proper descaling reagent, self-generated oxidation-induced copper coating appeared on the steel surface. The method proposed in this work is environmentally friendly for nontoxic chemicals being used. In addition, this provides a new concept for producing protective composite by oxidizing from the substrate directly and there is no bonding problem.

Periodate – an alternative oxidant for testing potential water oxidation catalysts

The redox catalyst ruthenium dioxide, prepared via the Adams technique, i.e.Ru(Adams), is used as a water oxidation catalyst using the oxidants (i) Ce(IV) in 0.5M H2SO4 and (ii) periodate in 0.5 M H2SO4, water and 0.1 M KOH. Like Ce(IV),periodate is a very strong oxidant that is able to oxidise water to oxygen and can bereadily monitored spectrophotometrically at 280 nm, compared with 430 nm for Ce(IV).More importantly, unlike Ce(IV), which is unstable towards hydrolysis above pH 1,periodate is stable in acid, water and strong alkali. A spectrophotometric study of thekinetics of periodate reduction, and concomitant oxidation of water to O2, reveals thatin the presence of a suitable redox catalyst, Ru(Adams) in this work, periodate is ableto effect the stoichiometric oxidation of water, with a turnover number > 64. In justwater, the kinetics of the latter reaction appear diffusion-controlled, due to the largethermodynamic driving force, a measure of which is the difference in redox potential,i.e. ∆E = 423 mV. As this difference is decreased, ∆E = 396 mV in acid and 290 mVin strong alkali (0.1 M KOH), the kinetics become increasingly activation-controlledand slower. These findings are discussed briefly with regard to the possible use of (i)periodate as an alternative oxidant in the rapid screening of new potential wateroxidation catalyst material powders that are stable only under near neutral and/oralkaline conditions, and (ii) Ru(Adams) as a benchmark catalyst.

Application of a cw quantum cascade laser CO2 analyser to catalytic oxidation reaction monitoring

Catalytic oxidation reaction monitoring has been performed for the first time with a trace gas carbon dioxide analyser based on a continuous wave (cw), thermoelectrically cooled (TEC), distributed feedback (DFB) quantum cascade laser (QCL) operating at around 2307 cm^-1. The reaction kinetics for carbon monoxide oxidation over a platinum catalyst supported on yttria-stabilised zirconia were followed by the QCL CO₂ analyser and showed that it is a powerful new tool for measuring low reaction rates associated with low surface area model catalysts operating at atmospheric pressures. A detection limit was determined of 40 ppb (1 standard deviation) for a 0.1 s average and a residual absorption standard deviation of 1.9×10^-4. © 2012 Springer-Verlag.

Comparative studies between classic and wireless electrochemical promotion of a Pt catalyst for ethylene oxidation

A comparative study between a classic and a wireless electrochemical promotion experiment was undertaken as a tool towards the better understanding of both systems. The catalytic modification of a platinum catalyst for ethylene oxidation was studied. The catalyst was supported on yttria-stabilised-zirconia (YSZ), a known pure oxide ion conductor, for the classic experiment and La _0.6Sr_0.4Co_0.2Fe_0.8O _3-δ-a mixed oxide ion electronic conductor-was used for the wireless experiment. The two systems showed certain similarities in terms of the reaction classification (in both cases electrophobic behaviour was observed) and the promotion mechanism. Significant difference was observed in the time scales and the reversibility of the induced rate modification. © 2008 Springer Science+Business Media B.V.

Understanding Complete Oxidation of Methane on Spinel Oxides at Molecular Level

It is crucial to develop a catalyst made of earth-abundant elements highly active for a complete oxidation of methane at a relatively low temperature. NiCo₂O₄ consisting of earth-abundant elements which can completely oxidize methane in the temperature range of 350-550 °C. Being a cost-effective catalyst, NiCo₂O₄ exhibits activity higher than precious-metal-based catalysts. Here we report that the higher catalytic activity at the relatively low temperature results from the integration of nickel cations, cobalt cations and surface lattice oxygen atoms/oxygen vacancies at the atomic scale. In situ studies of complete oxidation of methane on NiCo₂O₄ and theoretical simulations show that methane dissociates to methyl on nickel cations and then couple with surface lattice oxygen atoms to form -CH₃O with a following dehydrogenation to -CH₂O; a following oxidative dehydrogenation forms CHO; CHO is transformed to product molecules through two different sub-pathways including dehydrogenation of OCHO and CO oxidation.

Methanol electro-oxidation on platinum modified tungsten carbides in direct methanol fuel cells: a DFT study

In exploration of low-cost electrocatalysts for direct methanol fuel cells (DMFCs), Pt modified tungsten carbide (WC) materials are found to be great potential candidates for decreasing Pt usage whilst exhibiting satisfactory reactivity. In this work, the mechanisms, onset potentials and activity for electrooxidation of methanol were studied on a series of Pt-modified WC catalysts where the bare W-terminated WC(0001) substrate was employed. In the surface energy calculations of a series of Pt-modified WC models, we found that the feasible structures are mono- and bi-layer Pt-modified WCs. The tri-layer Pt-modified WC model is not thermodynamically stable where the top layer Pt atoms tend to accumulate and form particles or clusters rather than being dispersed as a layer. We further calculated the mechanisms of methanol oxidation on the feasible models via methanol dehydrogenation to CO involving C-H and O-H bonds dissociating subsequently, and further CO oxidation with the C-O bond association. The onset potentials for the oxidation reactions over the Pt-modified WC catalysts were determined thermodynamically by water dissociation to surface OH* species. The activities of these Pt-modified WC catalysts were estimated from the calculated kinetic data. It has been found that the bi-layer Pt-modified WC catalysts may provide a good reactivity and an onset oxidation potential comparable to pure Pt and serve as promising electrocatalysts for DMFCs with a significant decrease in Pt usage.

Lower resting energy expenditure and fat oxidation in Native American and Hispanic infants born to mothers with diabetes

OBJECTIVE: To determine whether exposure to diabetes in utero affects resting energy expenditure (REE) and fuel oxidation in infants.

STUDY DESIGN: At 35 ± 5 days after birth, body composition and REE were measured in full-term offspring of Native American and Hispanic women with either well-controlled diabetes (13 girls, 11 boys) or normal healthy pregnancies (18 girls, 17 boys).

RESULTS: Control of dysglycemia during gestation in the women with diabetes mellitus met current clinical standards, shown by average glycated hemoglobin (5.9 ± 0.2%; 40.6 ± 2.3 mmol/mol). Infant body mass (offspring of women with diabetes: 4.78 ± 0.13, control offspring: 4.56 ± 0.08 kg) and body fatness (offspring of women with diabetes: 25.2 ± 0.6, control offspring: 24.2 ± 0.5 %) did not differ between groups. REE, adjusted for lean body mass, was 14% lower in offspring of women with diabetes (41.7 ± 2.3 kJ/h) than control offspring (48.6 ± 2.0, P = .025). Fat oxidation was 26% lower in offspring of women with diabetes (0.54 ± 0.05 g/h) than control offspring (0.76 ± 0.04, P < .01) but carbohydrate oxidation did not differ. Thus, fat oxidation accounted for a lower fraction of REE in the offspring of women with diabetes (49 ± 4%) than control offspring (60 ± 3%, P = .022). Mothers with diabetes were older and had higher prepregnancy body mass index than control mothers.

CONCLUSIONS: Well-controlled maternal diabetes did not significantly affect body mass or composition of offspring at 1-month old. However, infants with mothers with diabetes had reduced REE and fat oxidation, which could contribute to adiposity and future disease risk. Further studies are needed to assess the impact differences in age and higher prepregnancy body mass index.