Iron(III) Porphyrin Covalently Supported onto Magnetic Amino-Functionalized Nanospheres as Catalyst for Hydrocarbon and Herbicide Oxidations

This work describes the covalent immobilization of an ironporphyrin, 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin iron(III) chloride (FeTFPP), onto maghemite/silica magnetic nanospheres covered with aminofunctionalized silica. The resulting material (gamma-Fe2O3/SiO2-NHFeP) was characterized by diffuse reflectance infrared spectroscopy (DRIFTS) and UV-Vis absorption spectroscopy. The catalytic activity of this magnetic ironporphyrin was investigated in the oxidation of hydrocarbons (styrene, (Z)-cyclooctene and R-(+)-limonene) and an herbicide (simazine) by hydrogen peroxide or 3-chloroperoxybenzoic acid. Hydrocarbon and simazine oxidation reaction products were analyzed by gas chromatography (GC) and high performance liquid chromatography (HPLC), respectively. This catalytic system proved to be efficient and selective for hydrocarbon oxidation, leading to high product yields from styrene (89%), cyclooctene (71%) and R-(+) -limonene (86%). Simazine oxidation was attained with 100% selectivity for a dechlorinated product (OEAT), while several oxidation products were obtained for the same catalyst in homogeneous media. The catalyst can be easily recovered through application of an external magnetic field and washed after reaction. Catalyst reuse experiments for R-(+)-limonene oxidation have shown that the catalytic activity is kept at 90% after 10 consecutive reactions.

Iron(III) porphyrin covalently supported onto magnetic amino-functionalized nanospheres as catalyst for hydrocarbon and herbicide oxidations

This work describes the covalent immobilization of an ironporphyrin, 5,10,15,20- tetrakis(pentafluorophenyl)porphyrin iron(III) chloride (FeTFPP), onto maghemite/silica magnetic nanospheres covered with aminofunctionalized silica. The resulting material (γ-Fe2O3/SiO2-NHFeP) was characterized by diffuse reflectance infrared spectroscopy (DRIFTS) and UV-Vis absorption spectroscopy. The catalytic activity of this magnetic ironporphyrin was investigated in the oxidation of hydrocarbons (styrene, (Z)-cyclooctene and R-(+)-limonene) and an herbicide (simazine) by hydrogen peroxide or 3-chloroperoxybenzoic acid. Hydrocarbon and simazine oxidation reaction products were analyzed by gas chromatography (GC) and high performance liquid chromatography (HPLC), respectively. This catalytic system proved to be efficient and selective for hydrocarbon oxidation, leading to high product yields from styrene (89%), cyclooctene (71%) and R-(+)-limonene (86%). Simazine oxidation was attained with 100% selectivity for a dechlorinated product (OEAT), while several oxidation products were obtained for the same catalyst in homogeneous media. The catalyst can be easily recovered through application of an external magnetic field and washed after reaction. Catalyst reuse experiments for R-(+)-limonene oxidation have shown that the catalytic activity is kept at 90% after 10 consecutive reactions.

The impact of the alkali cation on the mechanism of the electro-oxidation of ethylene glycol on Pt

By means of in situ IR spectroscopy we investigate the effect of dissolved alkali cations on the electro-oxidation of ethylene glycol on platinum in alkaline media. The results revealed that the increase in the oxidation currents (Li(+) < Na(+) < K(+)) is reflected in the increase in the ratio between carbonate and oxalate produced.

Diversity of hydrocarbon-degrading Klebsiella strains isolated from hydrocarbon-contaminated estuaries

To investigate the diversity and the catabolic capacity of oil-degrading Klebsiella strains isolated from hydrocarbon-contaminated sediments in Santos-Sao Vicente estuary systems in Brazil. Klebsiella strains obtained from the estuary were characterized using 16S rRNA gene sequencing and BOX-PCR patterns, testing their catabolic capacity to degrade toluene, xylene, naphthalene and nonane, and identifying the catabolic genes present in the oil-degrading strains. Results show that Klebsiella strains were widespread in the estuary. Twenty-one isolates from the Klebsiella genus were obtained; 14 had unique BOX patterns and were further investigated. Among four distinct catabolic genes tested (todC1, ndoB, xylE and alkB1), only the todC1 gene could be amplified in two Klebsiella strains. The biodegradation assay showed that most of the strains had the ability to degrade all of the tested hydrocarbons; however, the strains displayed different efficiencies. The oil-degrading Klebsiella isolates obtained from the estuary were closely related to Klebsiella pneumoniae and Klebsiella ornithinolytica. The isolates demonstrated a substantial degree of catabolic plasticity for hydrocarbon degradation. The results of this study show that several strains from the Klebsiella genus are able to degrade diverse hydrocarbon compounds. These findings indicate that Klebsiella spp. can be an important part of the oil-degrading microbial community in estuarine areas exposed to sewage.

Results from a 15-year study on hydrocarbon concentrations in water and sediment from Admiralty Bay, King George Island, Antarctica

Admiralty Bay on the King George Island hosts the Brazilian, Polish and Peruvian research stations as well as the American and Ecuadorian field stations. Human activities in this region require the use of fossil fuels as an energy source, thereby placing the region at risk of hydrocarbon contamination. Hydrocarbon monitoring was conducted on water and sediment samples from the bay over 15 years. Fluorescence spectroscopy was used for the analysis of total polycyclic aromatic hydrocarbons (PAHs) in seawater samples and gas chromatography with flame ionization and/or mass spectrometric detection was used to analyse individual n-alkanes and PAHs in sediment samples. The results revealed that most sites contaminated by these Compounds are around the Brazilian and Polish research stations due to the intense human activities, mainly during the summer. Moreover, the sediments revealed the presence of hydrocarbons from different sources, suggesting a mixture of the direct input of oil or derivatives and derived from hydrocarbon combustion. A decrease in PAH concentrations occurred following improvement of the sewage treatment facilities at the Brazilian research station, indicating that the contribution from human waste may be significant.

Electrocatalytic Activity of Platinum-Niobium Nanoparticles for Ethanol Oxidation

Three nanostructured platinum-niobium supported on Vulcan XC-72R carbon black materials were prepared as catalysts for the ethanol electroxidation: (i) deposition of platinum and niobium on Vulcan XC-72R carbon black, (ii) platinum decorated on a mixture of commercial amorphous Nb2O5/carbon black, and (iii) the same than ii but using crystalline Nb2O5, by reduction of the precursors with sodium borohydride in ethanol. All the catalysts showed platinum crystal sizes in the range of 3-4 nm, with no or little modification of the lattice parameter. The analyses of the electronic structure from the XANES region of the XAS spectra displayed some interactions between platinum and niobium, despite the niobium was primarily in the form of pentoxide in all the catalysts. CO stripping exhibited a promising low onset potential and a large current density, especially in the case of the deposited catalyst. Ethanol electroxidation experiments revealed that the Pt-Nb(2)O(5)crystalline/C generated the largest current. However it was not effective to completely oxidize ethanol, leading to acetic acid as the main product. In this sense, the highest efficiency for the complete oxidation of ethanol was obtained for the deposited catalyst. These results were interpreted in terms of the physico-chemical characteristic displayed by the different catalysts. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.040210jes] All rights reserved.

On the stability of the extracellular hemoglobin of Glossoscolex paulistus, in two iron oxidation states, in the presence of urea

The stability of the Glossoscolex paulistus hemoglobin (HbGp), in two iron oxidation states (and three forms), as monitored by optical absorption, fluorescence emission and circular dichroism (CD) spectroscopies, in the presence of the chaotropic agent urea, is studied. HbGp oligomeric dissociation, denaturation and iron oxidation are observed. CD data show that the cyanomet-HbGp is more stable than the oxy-form. Oxy- and cyanomet-HbGp show good fits on the basis of a two state model with critical urea concentrations at 220-222 nm of 5.1 +/- 0.2 and 6.1 +/- 0.1 mol/L, respectively. The three-state model was able to reveal a subtle second transition at lower urea concentration (1.0-2.0 mol/L) associated to partial oligomeric dissociation. The intermediate state for oxy- and cyanomet-HbGp is very similar to the native state. For met-HbGp, a different equilibrium, in the presence of urea, is observed. A sharp transition at 1.95 +/- 0.05 mol/L of denaturant is observed, associated to oligomeric dissociation and hemichrome formation. In this case, analysis by a three-state model reveals the great similarity between the intermediate and the unfolded states. Analysis of spectroscopic data, by two-state and three-state models, reveals consistency of obtained thermodynamic parameters for HbGp urea denaturation. (C) 2012 Elsevier Inc. All rights reserved.

Electrocatalytic performance of environmentally friendly synthesized gold nanoparticles towards the borohydride electro-oxidation reaction

In this paper we report a simple and environmentally friendly synthesis of gold nanoparticles (AuNps) and their electrocatalytic activity for borohydride oxidation reaction (BOR). Ultraviolet spectroscopy (UV- vis) and transmission electron microscopy (TEM) confirmed the formation of poly(vinyl pyrrolidone)protected colloidal AuNps through direct reduction of Au3+ by glycerol in alkaline medium at room temperature. For the BOR tests the AuNps were directly produced onto carbon to yield the Au/C catalyst. Levich plots revealed that the process occured via 7.2 electrons, therefore near the theoretical value of 8 electrons. When compared to bulk Au, the gold nanoparticles presented enhanced catalytic properties since the onset potential for BOR was shifted 200 mV towards negative potentials. (C) 2012 Elsevier B.V. All rights reserved.

Partial oxidation of methane on NiO-MgO-ZrO2 catalysts

Catalysts containing mixtures of NiO, MgO and ZrO2 were synthesized by the polymerization method. They were characterized by X-ray diffraction (XRD), physisorption of N-2 (BET), X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES), and then tested in the partial oxidation of methane (POM) in the presence of air (2CH(4):1O(2)) at 750 degrees C for 6 h. Among the ternary oxides, the catalyst with 40 mol% MgO showed the highest conversion rates in the catalytic processes, but also the highest carbon deposition values (48 mmol h (1)). The greater the amount of NiO-MgO solid solution formed, the higher was the conversion rate of reactants (CH4), peaking at 40 mol% of MgO. Catalysts with lower Ni content on the surface achieved a high rate of CH4 conversion into synthesis gas (H-2 + CO). The formation of more NiO-MgO solid solution seemed to inhibit the deactivation of Ni degrees during reaction. The values of the H-2/CO product ratio were generally found to be slightly lower than stoichiometric. (C) 2012 Elsevier Ltd. All rights reserved.

Photo-Fenton oxidation of phenol and organochlorides (2,4-DCP and 2,4-D) in aqueous alkaline medium with high chloride concentration

A highly concentrated aqueous saline-containing solution of phenol, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenol (2.4-DCP) was treated by the photo-Fenton process in a system composed of an annular reactor with a quartz immersion well and a medium-pressure mercury lamp (450 W). The study was conducted under special conditions to minimize the costs of acidification and neutralization, which are usual steps in this type of process. Photochemical reactions were carried out to investigate the influence of some process variables such as the initial concentration of Fe2+ ([Fe2+](0)) from 1.0 up to 2.5 mM, the rate in mmol of H2O2 fed into the system (F-H2O2,F-in) from 3.67 up to 7.33 mmol of H2O2/min during 120 min of reaction time, and the initial pH (pH(0)) from 3.0 up to 9.0 in the presence and absence of NaCl (60.0 g/L). Although the optimum pH for the photo-Fenton process is about 3.0, this particular system performed well in experimental conditions starting at alkaline and neutral pH. The results obtained here are promising for industrial applications, particularly in view of the high concentration of chloride, a known hydroxyl radical scavenger and the main oxidant present in photo-Fenton processes. (C) 2012 Elsevier Ltd. All rights reserved.

A comparative study of the electrochemical oxidation of the herbicide tebuthiuron using boron-doped diamond electrode

The thiadiazolylurea derivative tebuthiuron (TBH) is commonly used as an herbicide even though it is highly toxic to humans. While various processes have been proposed for the removal of organic contaminants of this type from wastewater, electrochemical degradation has shown particular promise. The aim of the present study was to investigate the electrochemical degradation of TBH using anodes comprising boron-doped (5000 and 30000 ppm) diamond (BDD) films deposited onto Ti substrates operated at current densities in the range 10-200 mA cm(-2). Both anodes removed TBH following a similar pseudo first-order reaction kinetics with k(ap)p close to 3.2 x 10(-2) min(-1). The maximum mineralization efficiency obtained was 80%. High-pressure liquid chromatography with UV-VIS detection established that both anodes degraded TBH via similar intermediates. Ion chromatography revealed that increasing concentrations of nitrate ions (up to 0.9 ppm) were formed with increasing current density, while the formation of nitrite ions was observed with both anodes at current densities >= 150 mA cm(-2). The BDD film prepared at the lower doping level (5000 ppm) was more efficient in degrading TBH than its more highly doped counterpart. This unexpected finding may be explained in terms of the quantity of impurities incorporated into the diamond lattice during chemical vapor deposition. (C) 2012 Elsevier Ltd. All rights reserved.

Synthesis of Carbon Nanomaterials through Up-Cycling Agricultural and Municipal Solid Wastes

This work addresses the synthesis of carbon nanomaterials (CNMs) by up-cycling common solid wastes. These feedstocks could supersede the use of costly and often toxic or highly flammable chemicals, such as hydrocarbon gases, carbon monoxide, and hydrogen, which are commonly used as feedstocks in current nanomanufacturing processes for CNMs. Agricultural sugar cane bagasse and corn residues, scrap tire chips, and postconsumer polyethylene (PE) and polyethylene terephthalate (PET) bottle shreddings were either thermally treated by sole pyrolysis or by sequential pyrolysis and partial oxidation. The resulting gaseous carbon-bearing effluents were then channeled into a heated reactor. CNMs, including carbon nanotubes, were catalytically synthesized therein on stainless steel meshes. This work revealed that the structure of the resulting CNMs is determined by the feedstock type, through the disparate mixtures of carbon-bearing gases generated when different feedstocks are pyrolyzed. CNM characterization was conducted by scanning and transmission electron microscopy as well as by Raman spectroscopy and by thermogravimetric analysis. Gas chromatography was used to characterize the gases in the synthesis chamber. This work demonstrated an alternative method for efficient manufacturing of CNMs using both biodegradable and nonbiodegradable agricultural and municipal carbonaceous wastes.

Effects of catalyst load in Pt and Pb-based catalysts using formic acid oxidation as a model

In this paper, we discuss the effects of catalyst load with respect to carbon powder for several Pt and Pb-based catalysts, using formic acid as a model molecule. The discussion is based on electrochemical tests, a complete morphological investigation and theoretical calculations. We show that the Pt and Pb-based catalysts presented activity in formic acid oxidation at very low catalyst loads (e.g., 0.5% in respect to the carbon content). Physical characterisations demonstrate that the electrodes are composed of separated phases of Pt and lead distributed in Pt nanometric-sized islands that are heterogeneously dispersed on the carbon support and Pb ultra-small particles homogeneously distributed throughout the entire carbon surface, as demonstrated by the microscopy studies. At high catalyst loads, very large clusters of Pb(x)O(y) could be observed. Electrochemical tests indicated an increase in the apparent resistance of the system (by a factor of 19.7 Omega) when the catalyst load was increased. The effect of lead in the materials was also studied by theoretical calculations (OFT). The main conclusion is that the presence of Pb atoms in the catalyst can improve the adsorption of formic acid in the catalytic system compared with a pure Pt-based catalyst. (C) 2011 Elsevier B.V. All rights reserved.

Combustion of coal, bagasse and blends thereof Part II: Speciation of PAH emissions

This work reports on emissions of unburned hydrocarbon species from batch combustion of fixed beds of coal, sugar-cane bagasse, and blends thereof in a pre-heated two-stage laboratory furnace operated in the temperature range of 800-1000 degrees C. The effects of fuel blending, combustion staging, and operating furnace temperatures on emissions of pollutants were assessed. Furnace effluents were analyzed for products of incomplete combustion (PICs) including CO, volatile and semi-volatile hydrocarbons, and particulate matter, as has been reported in Ref. [1]. Emitted unburned hydrocarbons include traces of potentially health-hazardous Polycyclic Aromatic Hydrocarbons (PAHs), which are the focus of this work. Under the batch combustion conditions implemented herein, PAH were only generated during the volatile combustion phase of the fuels. The most prevalent species were in descending order: naphthalene, acenaphthylene, phenanthrene, fluoranthene, pyrene, dibenzofuran, benzofuran, byphenyl, fluorene, 9H-fluoren-9-one, acephenantrylene, benzo[b] fluoranthene, 1-methyl-naphthalene; 2-methyl-naphthalene, benz[a] anthracene and benzo[a] pyrene. PAH yields were the highest from combustion of neat bagasse. Combustion of the blends resulted in lower yields of PAH, than combustion of either of their neat fuel constituents. Increasing the furnace operating temperature enhanced the PAH emissions from bagasse, but had little effect on those from the coal or from the blends. Flue gas treatment in a secondary-stage furnace, upon with additional air, typically reduced PAH yields by promoting oxidation of the primary-stage furnace effluents. (C) 2011 Elsevier Ltd. All rights reserved.

Cytochrome c-promoted cardiolipin oxidation generates singlet molecular oxygen

The interaction of cytochrome c (cyt c) with cardiolipin (CL) induces protein conformational changes that favor peroxidase activity. This process has been correlated with CL oxidation and the induction of cell death. Here we report evidence demonstrating the generation of singlet molecular oxygen [O-2((1)Delta(g))] by a cyt c-CL complex in a model membrane containing CL. The formation of singlet oxygen was directly evidenced by luminescence measurements at 1270 nm and by chemical trapping experiments. Singlet oxygen generation required cyt c-CL binding and occurred at pH values higher than 6, consistent with lipid-protein interactions involving fully deprotonated CL species and positively charged residues in the protein. Moreover, singlet oxygen formation was specifically observed for tetralinoleoyl CL species and was not observed with monounsaturated and saturated CL species. Our results show that there are at least two mechanisms leading to singlet oxygen formation: one with fast kinetics involving the generation of singlet oxygen directly from CL hydroperoxide decomposition and the other involving CL oxidation. The contribution of the first mechanism was clearly evidenced by the detection of labeled singlet oxygen [O-18(2)((1)Delta(g))] from liposomes supplemented with 18-oxygen-labeled CL hydroperoxides. However quantitative analysis showed that singlet oxygen yield from CL hydroperoxides was minor (<5%) and that most of the singlet oxygen is formed from the second mechanism. Based on these data and previous findings we propose a mechanism of singlet oxygen generation through reactions involving peroxyl radicals (Russell mechanism) and excited triplet carbonyl intermediates (energy transfer mechanism).