Advances in ethanol reforming for the production of hydrogen

Catalytic steam reforming of ethanol (SRE) is a promising route for the production of renewable hydrogen (H2). This article reviews the influence of doping supported-catalysts used in SRE on the conversion of ethanol, selectivity for H2, and stability during long reaction periods. In addition, promising new technologies such as membrane reactors and electrochemical reforming for performing SRE are presented.

Estudo de catalisadores de níquel suportados em cinza de casca de arroz na reforma de metano com dióxido de carbono visando a produção de hidrogênio e gás de síntese

Rice husk ash (RHA) is used as a silica source for several purposes, among them to obtain metal catalysts, as was done in this work. The catalysts were characterized by chemisorption, physisorption, thermal analyses (TG, DSC), X-ray diffraction, X-ray fluorescence, temperature-programmed reduction and scanning electron microscopy. The catalysts synthesized with different Ni loadings supported on RHA were applied to the reaction of dry reforming of methane. The reaction was tested at three temperatures of catalytic reduction (500, 600 and 700 ºC). All synthesized catalysts were active for the studied reaction, with different H2/CO ratios achieved according to degree of metallic dispersion.

SÍNTESE E CARACTERIZAÇÃO DE COMPÓSITOS ORGÂNICO-INORGÂNICOS MACROPOROSOS PARA O SENSORIAMENTO DE H2O2

Electrodes modified with poly(5-amino-1-naphthol)/Prussian blue (poly(5-NH2-1-NAP)/PB) hybrid films are able to electrochemically reduce H2O2 in medium containing an excess of Na+ cations. This is an important advantage for biosensing applications over electrodes in which only conventionally (electro) deposited Prussian blue is present. Consequently, the aim of this work was to examine the application of templates of ordered arrays of colloidal poly(styrene) spheres (800, 450 and 100 nm in diameter) to produce inverse opal structures of poly(5-NH2-1-NAP)/PB hybrid platforms, in an effort to study the influence of the increase in surface area/volume ratio and higher exposition of the mediator active sites on material performance during H2O2 determination employing the different sized porous structures. Moreover, since the accentuated hydrophilic character of poly(5-NH2-1-NAP)/PB also allows H2O2 electrochemical reduction in inner active sites, issues concerning the amount of mediator electrodeposited on the electrode were also reflected in the observed results.

A FTIR study of the metal-support interactions and hydrogen spillover on Pd/TiO2 and Ni/TiO2

Nickel and palladium dispersed on titania support were submitted to reductive treatment, under hydrogen, at 200 and 500 ºC. After the reductive thermal treatment the materials were exposed to carbon monoxide (10 Torr) and analyzed in the infrared region. The increasing of the electronic density in the metallic d subshell, produced by the reductive thermal treatment, was monitored by the infrared stretching band shift of carbon monoxide adsorbed and it was interpreted as a consequence of the metal-support interactions. The highest effect was observed for Pd/TiO2 system. From the FTIR spectra was also observed that the hydrogen spillover was stronger on Pd/TiO2 than Ni/TiO2 system.

Electrochemical and physical characterization of Ni-Cu-Fe alloy for chlor-alkali hydrogen cathodes

This work describes the development of an alternative acetate bath for the electrochemical codeposition of Ni-Cu-Fe electrodes at low pH that is stable for several weeks and produces electrodes with good performance for chlor-alkali electrolysis. Physical characterization of the electrode surface was made using X ray absorption spectroscopy (XAS), scanning electron microscopy (SEM) and energy dispersive analysis (EDX). The evaluation of the material as electrocatalyst for the hydrogen evolution reaction (her) was carried out in brine solution (160 g L-1 NaCl + 150 g L-1 NaOH) at different temperatures through steady-state polarization curves. The Ni-Cu-Fe electrodes obtained with this bath have shown low overpotentials for the her, around 0.150 V at 353 K, and good stability under continuous long-term operation for 260 hours. One positive aspect of this cathode is that the polarization behavior of the material shows only one Tafel slope over the temperature range of 298 - 353 K.

Evaluation of gas diffusion electrodes as detectors in amperometric hydrogen sensors

This work is directed to the study and evaluation of gas diffusion electrodes as detectors in hydrogen sensors. Electrochemical experiments were carried out with rotating disk electrodes with a thin porous coating of the catalyst as a previous step to select useful parameters for the sensor. An experimental arrangement made in the laboratory that simulates the sensor was found appropriate to detect volumetric hydrogen percentages above 0.25% in mixtures H2:N2. The system shows a linear response for volumetric percentages of hydrogen between 0.25 and 2 %.

Electrochemical evidence of sulfinic acid derivative as an intermediate in the reduction of aromatic sulfonyl chloride in an aprotic medium

The electrochemical reduction of p-nitrobenzenesulfonyl chloride (NBSCl) in dimethylsulfoxide (DMSO) solution is used here as a model to investigate the role of sulfinic acid derivative in this compound's global reduction process. Cyclic voltammetric experiments reveal the production of sulfinic acid derivative, which is important in chemical reactions involving the original compound and other intermediates. This paper also discusses the probable mechanisms of the reduction.

Self-assembly of supermolecular species directed by hydrogen bonding and aromatic π-π stacking interactions

A new Cu(II) trimers, [Cu3(dcp)2(H2O)8]. 4DMF, with the ligand 3,5-pyrazoledicarboxylic acid monohydrate (H3dcp) has been prepared by solvent method. Its solid-state structure has been characterized by elemental analysis, thermal analysis (TGA and DSC), and single crystal X-ray diffraction. X-ray crystallographic studies reveal that this complex has extended 1-D,2-D and 3-D supramolecular architectures directed by weak interactions (hydrogen bond and aromatic π-π stacking interaction) leading to a sandwich solid-state structure.

A simple spectrophotometric method for the determination of methyldopa using p-chloranil in the presence of hydrogen peroxide

A simple, rapid and sensitive spectrophotometric method has been developed for the determination of methyldopa in pharmaceutical formulations. The method is based on the reaction between tetrachloro-p-benzoquinone (p-chloranil) and methyldopa, accelerated by hydrogen peroxide (H2O2), producing a violet-red compound (λmax = 535 nm) at ambient temperature (25.0 ± 0.2 ºC). Experimental design methodologies were used to optimize the measurement conditions. Beer's law is obeyed in a concentration range from 2.10 x 10-4 to 2.48 x 10-3 mol L-1 (r = 0.9997). The limit of detection was 7.55 x 10-6 mol L-1 and the limit of quantification was 2.52 x 10-5 mol L-1. The intraday precision and interday precision were studied for 10 replicate analyses of 1.59 x 10-3 mol L-1 methyldopa solution and the respective coefficients of variation were 0.7 and 1.1 %. The proposed method was successfully applied to the determination of methyldopa in commercial brands of pharmaceuticals. No interferences were observed from the common excipients in the formulations. The results obtained by the proposed method were favorably compared with those given by the Brazilian Pharmacopoeia procedure at 95 % confidence level.

Adsorption isotherm studies of BOD, TSS and colour reduction from palm oil mill effluent (POME) using boiler fly ash

Palm oil is one of the two most important vegetable oils in the world's oil and fats market. The extraction and purification processes generate different kinds of waste generally known as palm oil mill effluent (POME). Earlier studies had indicated the possibility of using boiler fly ash to adsorb impurities and colour in POME treatment. The adsorption treatment of POME using boiler fly ash was further investigated in detail in this work with regards to the reduction of BOD, colour and TSS from palm oil mill effluent. The amount of BOD, colour and TSS adsorbed increased as the weight of the boiler fly ash used was increased. Also, the smaller particle size of 425µm adsorbed more than the 850µm size. Attempts were made to fit the experimental data with the Freundlich, Langmuir and Dubinin-Radushkevich isotherms. The R² values, which ranged from 0.8974-0.9898, 0.8848-0.9824 and 0.6235-0.9101 for Freundlich, Langmuir and Dubinin-Radushkevich isotherms respectively, showed that Freundlich isotherm gave a better fit followed by Langmuir and then Dubinin-Radushkevich isotherm. The sorption trend could be put as BOD > Colour > TSS. The apparent energy of adsorption was found to be 1.25, 0.58 and 0.97 (KJ/mol) for BOD, colour and TSS respectively, showing that sorption process occurs by physiosorption. Therefore, boiler fly ash is capable of reducing BOD, Colour and TSS from POME and hence could be used to develop a good adsorbent for POME treatment.

In vivo sensitivity reduction of Puccinia triticina races, causal agent of wheat leaf rust, to DMI and QoI fungicides

Experiments were carried out to determine in vivo the IC50 and the IC90 for demethylation-inhibitor fungicides (DMIs, triazoles) and quinone outside inhibitors (QoIs, strobilurins) to the five most frequent races of Puccinia triticina in 2007 growing season in Southern Brazil. The tests were done in a greenhouse with wheat seedlings. DMI fungicides were tested at the concentrations, in mg/L, 0.0; 0.02; 0.2; 2.0; 20.0; 100.0 and 200.0, and QoIs at the concentrations 0.0; 0.0001; 0.001; 0.01; 0.1; 1 and 10.0 mg of active ingredient/L water. Fungicides were preventively applied at 24 hours before the inoculation of seedlings with the fungal spores. The effect of treatments was assessed based on the number of uredia/cm². The lowest IC50 (inhibitory concentration) for DMI fungicides determined for MCG-MN, sensitive race, ranged from 0.33 to 0.91 mg/L, while the highest values for MDP-MR, MDT-MR, MDK-MR, MFH-HT races, varied from 9.63 to 85.64 mg/L (suspected insensitivity). QoI fungicide presented an IC50 varying from 0.0018 to 0.14 mg/L. The sensitivity reduction factor for DMIs varied from 8.8 to 238.8, and for QoIs from 0.3 to 1.5 mg/L. Sensitivity reduction was confirmed for the races MDP-MR, MDT-MR, MDK-MR, MFH-HT to DMIs, as well as their sensitivity to QoI fungicides.

Sensitivity reduction in Blumeria graminis f. sp. hordei to triadimenol fungicide applied as barley seed treatment

Experiments were carried out in a growth chamber with controlled temperature and photoperiod to test two populations of Blumeria graminis f. sp. hordei from Guarapuava, Paraná State, and Passo Fundo, Rio Grande do Sul State, Brazil. Treatments consisted in application of the fungicide triadimenol (Baytan 150 SC®) at three rates of its commercial formulation: 150, 250, 350 mL/100 Kg barley seeds. The experiments were conducted separately in a growth chamber for each population, adopting the same temperature and photoperiod. For inoculation, pots containing barley seedlings colonized by the fungus were placed among the plots. After emergence of the first symptoms, the disease severity was assessed at two-day intervals. The experiments were repeated twice for each fungus population. Data were expressed as area under the disease progress curve and as powdery mildew control by comparing the severity after the fungicide treatments to that of control. Data were subjected to analysis of variance and regression analysis; the area under the disease progress curve was also calculated. Comparing the data obtained in the present study with those reported in the literature and the control, the maximum value of 26.1% is considered insufficient to prevent the damages caused by the disease. The control response to the fungicide rate was significant. We can conclude that there was a reduction in the sensitivity of both B. graminis f.sp. hordei populations to the fungicide triadimenol, which explains the control failure observed in barley farms.

In vitro sensitivity reduction of Fusarium graminearum to DMI and QoI fungicides

In Brazil, Fusarium head blight (FHB) affecting wheat can cause up to 39.8% damage. Resistant cultivars are not available yet; thus, short-term disease control relies on the use of fungicides. The first step to improve control is to monitor fungal populations that are sensitivity to chemicals in order to achieve efficient FHB management. In vitro experiments were conducted to evaluate the inhibitory concentration (IC50) of fungicides for both mycelial growth and conidial germination of ten Fusarium graminearum isolates. The following demethylation inhibitor (DMI) fungicides were tested: metconazole, prothioconazole and tebuconazole. In addition, pyraclostrobin and trifloxystrobin were included, representing QoI fungicides, as well as three co-formulations containing metconazole + pyraclostrobin, prothioconazole + trifloxystrobin, and tebuconazole + trifloxystrobin. For mycelial growth, the overall mean IC50 of isolates was: metconazole 0.07, prothioconazole 0.1, and tebuconazole 0.19 mg/L. For the co-formulations, it was: prothioconazole + trifloxystrobin 0.08, tebuconazole + trifloxystrobin 0.12, and metconazole + pyraclostrobin 0.14 mg/L. Regarding spore germination inhibition, IC50 for prothioconazole + trifloxystrobin was 0.06, for tebuconazole + trifloxystrobin, 0.12 mg/L, for QoI alone pyraclostrobin, was 0.09, and for trifloxystrobin, 0.28 mg/L. There was a sensitivity shift among isolates and the highest fungitoxicity to F. graminearum was confirmed for prothioconazole, metconazole and tebuconazole .

Raw water use charge reduction for the rural sector in the PCJ Watershed

The deficient environmental preservation on agricultural properties has reflected in great soil losses for erosion and the high rate of sedimentation. Therefore, this work brings the application of software to demonstrate that planters can get benefits by the conservationist practices. The benefits will be obtained from the environment aspect (erosion and sedimentation control), as well as economical aspect (financial incentives). A proposal has been created by the Technical Chamber of Rural Water Use and Conservation (CT-Rural) to estimate the reduction in raw water use charge for the rural water users of the PCJ Watershed - this reduction is being possible since January 2007, at the PCJ Committee. The software develops a simple relationship, so that if the rural conservationist action goes more efficient, such as if the conserved rural area goes larger, then the reduction value will bring better benefits for the rural water users. Within the purposes of this study, there is the idealization of mechanisms that may support specific management matters related to the water users of federal rivers from the rural sector of PCJ Watershed.

Relative reduction in annual soil loss in micro watersheds due to the relief and forest cover

With the intense debate, in Brazil, between landowners and public agencies about the amount of area with forest cover needed in different regions, there is an increase of the need for provision of technical data used as a basis for decision making. One of the criteria to evaluate the effect of forest cover in protecting water resources is the soil loss, which leads to several consequences on the environment, including the silting of the rivers. Therefore, this study aimed to evaluate the reduction in the soil loss in micro watersheds with different reliefs, size and location of forest cover, in the Corumbataí River watershed, in the state of São Paulo, using the Revised Universal Soil Loss Equation (RUSLE) in a GIS environment. For this study, 18 watersheds in three degrees of slope were selected, and 20 scenarios for land-use were established, by analyzing the influence of the PPA size, and the size and the location of the Legal Reserve. The results showed that: a) the effect of forest cover in reducing annual soil loss varies depending on the average slope of the watershed; b) the PPA width must be determined taking into account the slope of the watershed; c) the Legal Reserve must be located along the PPA. These provide better results in reducing annual soil loss.