Vegetable Oil Derived Solvent, and Catalyst Free Click Chemistry'' Thermoplastic Polytriazoles

Azide-alkyne Huisgen click chemistry provides new synthetic routes for making thermoplastic polytriazole polymers-without solvent or catalyst. This method was used to polymerize three diester dialkyne monomers with a lipid derived 18 carbon diazide to produce a series of polymers (labelled C18C18, C18C9, and C18C4 based on monomer chain lengths) free of residual solvent and catalyst. Three diester dialkyne monomers were synthesized with ester chain lengths of 4, 9, and 18 carbons from renewable sources. Significant differences in thermal and mechanical properties were observed between C18C9 and the two other polymers. C18C9 presented a lower melting temperature, higher elongation at break, and reduced Young's modulus compared to C18C4 and C18C18. This was due to the odd-even effect induced by the number of carbon atoms in the monomers which resulted in orientation of the ester linkages of C18C9 in the same direction, thereby reducing hydrogen bonding. The thermoplastic polytriazoles presented are novel polymers derived from vegetable oil with favourable mechanical and thermal properties suitable for a large range of applications where no residual solvent or catalyst can be tolerated. Their added potential biocompatibility and biodegradability make them ideal for applications in the medical and pharmaceutical industries.

Identification of Sudan III-(deoxy)-guanosine adducts formed in situ in a reaction with no catalyst

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Glycerol dehydration catalyzed by MWW zeolites and the changes in the catalyst deactivation caused by porosity modification

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Use of high-resolution thermogravimetric analysis (HRTG) technique in spent FCC catalyst/Portland cement pastes

Thermogravimetric analysis is one of the most common instrumental techniques used for the characterization of pastes, mortars and concretes based on both calcium hydroxide and Portland cement. Important information about pozzolanic materials can be assessed concerning calcium hydroxide consumption and the formation of new hydrated products. Nevertheless, in some cases, problems associated with the overlapped decomposition processes for hydrates make the analysis of obtained data difficult. In this paper, the use of high-resolution thermogravimetric analysis, a powerful technique that allows separating decomposition processes in analysis of hydrated binders, was performed for spent FCC catalyst-Portland cement pastes. These pastes were monitored for 1, 4, 8 h and 1, 2, 3, 7 and 28 curing days. In order to study the influence of the pozzolanic material (spent FCC catalyst), Portland cement replacements of 5, 15 and 30 % by mass were carried out. The presence of spent FCC catalyst in blended pastes modified the amount and the nature of the formed hydrates, mainly ettringite and stratlingite.

Convenient synthesis of ketal derivatives from cubebin using amberlite as heterogeneous catalyst

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Structural study of copper oxide supported on a ceria-modified titania catalyst system

A structural study of CuO supported on a CeO2-TiO2 system was undertaken using X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) techniques. The results of XRD revealed the presence of only two phases, TiO2 anatase and CeO2 cerianite. A trend towards smaller TiO2 crystallites was observed when cerium content increased. When the amount of cerium increased, Ti K-edge XANES analysis showed an increasing distortion of Ti sites. The results of Ce LIII-edge EXAFS showed that Ce atoms are coordinated by eight oxygen atoms at 2.32 Å. For the sample containing a small amount of cerium, the EXAFS analysis indicated that the local structure around Ce atoms was highly distorted. The catalysts presented quite different Cu K-edge XANES spectra compared to the spectra of the CuO and Cu2O reference compounds. The Cu-O mean bond length was close to that of the CuO and the Cu atoms in the catalysts are surrounded by approximately four oxygen atoms in their first shell. Copper supported on the ceria-modified titania support catalysts displayed a better performance in the methanol dehydrogenation when compared to copper supported only on titania or on ceria. © 2002 Plenum Publishing Corporation.

Influência do método de preparação de eletrocatalisadores PtRu/C sobre a atividade catalítica frente à reação de oxidação de etanol em meio ácido

In this work the influence of variations in the borohydrate reduction method on the properties of PtRu/C electrocatalysts was investigated. The electrocatalysts were prepared using 1:1 ; 2:1; 5:1; 50:1 and 250:1 molar ratios of NaBH₄ to metals. The reduction was also performed by dripping or by fast addition of the solution. The results showed that PtRu nanoparticles obtained by fast addition had the smallest crystallite sizes. It was also noted that the catalytic activity increased as the borohydrate:metal molar ratio increased. The PtRu/C electrocatalyst (50:1) obtained by fast addition presented the best catalytic activity for ethanol electro-oxidation.

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.

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.

Electrooxidation of Ethanol on Pt and PtRu Surfaces Investigated by ATR Surface-Enhanced Infrared Absorption Spectroscopy

Herein, it was investigated for the first time the electro-oxidation of ethanol on Pt and PtRu electrodeposits in acidic media by using in situ surface enhanced infrared absorption spectroscopy with attenuated total reflection (ATR-SEIRAS). The experimental setup circumvents the weak absorbance signals related to adsorbed species, usually observed for rough, electrodeposited surfaces, and allows a full description of the CO coverage with the potential for both catalysts. The dynamics of adsorption-oxidation of CO was accessed by ATR-SEIRAS experiments (involving four ethanol concentrations) and correlated with expressions derived from a simple kinetic model. Kinetic analysis suggests that the growing of the CO adsorbed layer is nor influenced by the presence of Ru neither by the concentration of ethanol. The results suggest that the C-C scission is not related to the presence of Ru and probably happens at Pt sites.

Effect of the relationship between particle size, inter-particle distance, and metal loading of carbon supported fuel cell catalysts on their catalytic activity

The effect of the relationship between particle size (d), inter-particle distance (x(i)), and metal loading (y) of carbon supported fuel cell Pt or PtRu catalysts on their catalytic activity, based on the optimum d (2.5-3 nm) and x(i)/d (>5) values, was evaluated. It was found that for y < 30 wt%, the optimum values of both d and x(i)/d can be always obtained. For y >= 30 wt%, instead, the positive effect of a thinner catalyst layer of the fuel cell electrode than that using catalysts with y < 30 wt% is concomitant to a decrease of the effective catalyst surface area due to an increase of d and/or a decrease of x(i)/d compared to their optimum values, with in turns gives rise to a decrease in the catalytic activity. The effect of the x(i)/d ratio has been successfully verified by experimental results on ethanol oxidation on PtRu/C catalysts with same particle size and same degree of alloying but different metal loading. Tests in direct ethanol fuel cells showed that, compared to 20 wt% PtRu/C, the negative effect of the lower x(i)/d on the catalytic activity of 30 and 40 wt% PtRu/C catalysts was superior to the positive effect of the thinner catalyst layer.

Oxygen reduction reaction on a Pt/carbon fuel cell catalyst in the presence of trace quantities of ammonium ions: An RRDE study

The effect of trace quantities of ammonia on oxygen reduction reaction (ORR) on carbon-supported platinum catalysts in perchloric acid solutions is assessed using rotating ring disk electrode (RRDE) technique. The study demonstrates that ammonia has detrimental effects on ORR. The most significant effect takes place in the potential region above 0.7 V vs RHE. The effect is explained by the electrochemical oxidation of ammonia, which blocks Pt active sites and increases the formation of H2O2. This leads to losses in the disk currents and increments in the ring currents. The apparent losses in ORR currents may occur in two ways, namely, through the blocking of the active sites for ORR as well as by generating a small anodic current, which is believed to have a lower contribution. In addition, a detrimental effect of sodium cations in the potential range below 0.75 V vs RHE was demonstrated. This effect is most likely due to the co-adsorption of sodium cations and perchlorate anions on the Pt surface. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Dilute Acid Hydrolysis of Sugar Cane Bagasse at High Temperatures: A Kinetic Study of Cellulose Saccharification and Glucose Decomposition. Part I: Sulfuric Acid as the Catalyst

The kinetics of sugar cane bagasse cellulose saccharification and the decomposition of glucose under extremely low acid (ELA) conditions, (0.07%), 0.14%, and 0.28% H2SO4, and at high temperatures were investigated using batch reactors. The first-order rate constants were obtained by weight loss, remaining glucose, and fitting glucose concentration profiles determined with HPLC using the Saeman model. The maximum glucose yields reached 67.6% (200 degrees C, 0.07% H2SO4, 30 min), 69.8% (210 degrees C, 0.14% H2SO4, 10 min), and 67.3% (210 degrees C, 0.28% H2SO4, 6 min). ELA conditions produced remarkable glucose yields when applied to bagasse cellulose. The first-order rate constants were used to calculate activation energies and extrathermodynamic parameters to elucidate the reaction mechanism under ELA conditions. The effect of acid concentration on cellulose hydrolysis and glucose decomposition was also investigated. The observed activation energies and reaction orders with respect to hydronium ion for cellulose hydrolysis and glucose decomposition were 184.9 and 124.5 kJ/mol and 1.27 and 0.75, respectively.

Performance and selectivity of PtxSn/C electro-catalysts for ethanol oxidation prepared by reduction with different formic acid concentrations

Carbon supported Pt-Sn catalysts were prepared by reduction of Pt and Sn precursors with formic acid and characterized in terms of structure, morphology and surface properties. The electrocatalytic activity for ethanol oxidation was studied in a direct ethanol fuel cell (DEFC) at 70 degrees C and 90 degrees C. Electrochemical and physico-chemical data indicated that a proper balance of Pt and Sn species in the near surface region was necessary to maximize the reaction rate. The best atomic surface composition, in terms of electrochemical performance, was Pt:Sn 65:35 corresponding to a bulk composition 75:25 namely Pt3Sn1/C. The reaction products of ethanol electro-oxidation in single cell and their distribution as a function of the nature of catalyst were determined. Essentially, acetaldehyde and acetic acid were detected as the main reaction products; whereas, a lower content of CO2 was formed. The selectivity toward acetic acid vs. acetaldehyde increased with the increase of the Sn content and decreased by decreasing the concentration of the reducing agent used in the catalyst preparation. According to the recent literature, these results have been interpreted on the basis of ethanol adsorption characteristics and ligand effects occurring for Sn-rich electrocatalysts. (C) 2012 Elsevier Ltd. All rights reserved.

Catalyst Recovery and Recycling Facilitated by Magnetic Separation: Iridium and Other Metal Nanoparticles

The immobilization of metal nanoparticles in magnetic responsive solids allows the easy, fast, and clean separation of catalysts; however, the efficiency of this separation process depends on a strong metalsupport interaction. This interaction can be enhanced by functionalizing the support surface with amino groups. Our catalyst support contains an inner core of magnetite that enables the magnetic separation from liquid systems and an external surface of silica suitable for further modification with organosilanes. We report herein that a magnetically recoverable amino-functionalized support captured iridium species from liquid solutions and produced a highly active hydrogenation catalyst with negligible metal leaching. An analogous Ir0 catalyst prepared with use of a nonfunctionalized support shows a higher degree of metal leaching into the liquid products. The catalytic performance in the hydrogenation of alkenes is compared with that of Rh and Pt catalysts.