Effect of presence of an acid catalyst on structure and properties of iron-doped siloxane-polyoxyethylene nanocomposites prepared by sol-gel

In this work we investigate the effect of hydrochloric acid (HC) addition on the structure and thermal and magnetic properties of iron-doped siloxane-polyoxyethylene (POE) hybrids prepared by the sol-gel route. X-ray powder diffraction (XRD) and X-ray absorption near edge structure (XANES) results reveal the dominance of ferrihydrite nanoparticles and a mixture of this phase with FeCl4- species in the hybrid prepared without and with HCl, respectively. Thermal analysis reveals the existence of two crystalline polymeric phases in the hybrid prepared with HCl whereas hybrids prepared without HCl are amorphous. The 105 and 60 Angstrom sized ferrihydrite nanoparticles were detected by SAXS analysis of the composite prepared without and with HCl, respectively. The magnetic results suggest that in both samples antiferromagnetic nanoparticles coexist with small clusters/isolated ions. In the sample without HCl addition, larger particles dominate the magnetic behavior, while the opposite occurs for the sample prepared using HCl catalyst. (C) 2004 Elsevier B.V. All rights reserved.

Construction and application of an electrochemical sensor for paracetamol determination based on iron tetrapyridinoporphyrazine as a biomimetic catalyst of P450 enzyme

This work describes the construction and application of a biomimetic sensor for paracetamol determination in different samples. The sensor was prepared by modifying a glassy carbon electrode surface with a Nafion (R) membrane doped with FeTPyPz. The best performance of the sensor in 0.1 mol L-1 acetate buffer was at pH 3.6. Under these conditions, an oxidation potential of paracetamol was observed at 445 mV vs. Ag vertical bar AgCl. The sensor presented a linear response range between 4.0 and 420 mu mol L-1, a sensitivity of 46.015 mA L mol(-1) cm(-2), quantification and detection limits of 4.0 mu mol L-1 and 1.2 mu mol L-1, respectively. A detailed investigation about its electrochemical behavior and selectivity was carried out. The results suggested that FeTPyPz presents catalytic properties similar to P450 enzyme for paracetamol oxidation. Finally, the sensor was applied for paracetamol determination in commercial drugs and for the monitoring of its degradation in an electrochemical batch reactor effluent.

Simultaneous solidification of two catalyst wastes and their effect on the early stages of cement hydration

Two catalyst wastes (RNi and RAI) from polyol production were considered as hazardous, due to their respective high concentration of nickel and aluminum contents. This article presents the study, done to avoid environmental impacts, of the simultaneous solidification/stabilization of both catalyst wastes with type II Portland cement (CP) by non-conventional differential thermal analysis (NCDTA). This technique allows one to monitor the initial stages of cement hydration to evaluate the accelerating and/or retarding effects on the process due to the presence of the wastes and to identify the steps where the changes occur. Pastes with water/cement ratio equal to 0.5 were prepared, into which different amounts of each waste were added. NCDTA has the same basic principle of Differential Thermal Analysis (DTA), but differs in the fact that there is no external heating or cooling system as in the case of DTA. The thermal effects of the cement paste hydration with and without waste presence were evaluated from the energy released during the process in real time by acquiring the temperature data of the sample and reference using thermistors with 0.03 A degrees C resolution, coupled to an analog-digital interface. In the early stages of cement hydration retarding and accelerating effects occur, respectively due to RNi and RAl presence, with significant thermal effects. During the simultaneous use of the two waste catalysts for their stabilization process by solidification in cement, there is a synergic resulting effect, which allows better hydration operating conditions than when each waste is solidified separately. Thermogravimetric (TG) and derivative thermogravimetric analysis (DTG) of 4 and 24 h pastes allow a quantitative information about the main cement hydrated phases and confirm the same accelerating or retarding effects due to the presence of wastes indicated from respective NCDTA curves.

Sulfur-containing palladacycles as catalyst precursors for the heck reaction

(formula presented) The air, water, and highly thermally stable sulfur-containing palladacycles, mainly derived from the ortho-palladation of benzylic thioethers, are exceptional catalyst precursors for the Heck reaction. The reaction can be performed with aryl iodides, bromides, and chlorides, with acrylic esters and styrene, leading to turnover numbers up to 1 850 000.

Sulfur-containing palladacycles: Efficient phosphine-free catalyst precursors for the Suzuki cross-coupling reaction at room temperature

Cyclopalladated compounds derived from the ortho-metalation of benzylic tert-butyl thioethers are excellent catalyst precursors for the Suzuki cross-coupling reaction of aryl bromides and chlorides with phenylboronic acid under mild reaction conditions. A broad range of substrates and functional groups are tolerated in this protocol, and highly catalytic activity is attained.

Photodegradation of soluble and emulsive cutting fluids using TiO 2 as catalyst

This paper describes results of the photo-degradation of three types of soluble and emulsive cutting fluids in an aqueous medium, using TiO2 as catalyst in suspension and UV radiation. The TiO2 proved to be an effective catalyst for the degradation of the cutting fluids investigated. The degradation rate depends on pH and nature of the fluids. The best performance of catalyst was observed at pH 8.0 for all the fluids when most of 70% of the organic load was decomposed. ©2006 Sociedade Brasileira de Química.

Sensor for diuron quantitation based on the P450 biomimetic catalyst nickel(II) 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine

A biomimetic sensor based on a carbon paste electrode modified with the nickel(II) 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine complex was developed as a reliable alternative technique for the sensitive and selective analysis of the herbicide diuron in environmental media. The sensor was evaluated using cyclic voltammetry and amperometric techniques. The best amperometric responses were obtained at 750 mV vs. Ag/AgCl (KClsat), using 0.1 mol L-1 phosphate buffer solution at pH 8.0. Under these conditions, the sensor showed a linear response for diuron concentrations between 9.9 × 10-6 and 1.5 × 10-4 mol L -1, a sensitivity of 22817 (±261) μA L mol-1, and detection and quantification limits of 6.14 × 10-6 and 2 × 10-5 mol L-1, respectively. The presence of the nickel complex in the carbon paste improved selectivity, stability, and sensitivity (which increased 700%), compared to unmodified paste. The applicability of the sensor was demonstrated using enriched environmental samples (river water and soil). © 2012 Elsevier B.V. All rights reserved.

Alkali activated materials based on fluid catalytic cracking catalyst residue (FCC): Influence of SiO2/Na2O and H 2O/FCC ratio on mechanical strength and microstructure

Reuse of industrial and agricultural wastes as supplementary cementitious materials (SCMs) in concrete and mortar productions contribute to sustainable development. In this context, fluid catalytic cracking catalyst residue (spent FCC), a byproduct from the petroleum industry and petrol refineries, have been studied as SCM in blended Portland cement in the last years. Nevertheless, another environmental friendly alternative has been conducted in order to produce alternative binders with low CO2 emissions. The use of aluminosilicate materials in the production of alkali-activated materials (AAMs) is an ongoing research topic which can present low CO2 emissions associated. Hence, this paper studies some variables that can influence the production of AAM based on spent FCC. Specifically, the influence of SiO 2/Na2O molar ratio and the H2O/spent FCC mass ratio on the mechanical strength and microstructure are assessed. Some instrumental techniques, such as SEM, XRD, pH and electrical conductivity measurements, and MIP are performed in order to assess the microstructure of formed alkali-activated binder. Alkali activated mortars with compressive strength up to 80 MPa can be formed after curing for 3 days at 65°C. The research demonstrates the potential of spent FCC to produce alkali-activated cements and the importance of SiO2/Na2O molar ratio and the H2O/spent FCC mass ratio in optimising properties and microstructure. © 2013 Elsevier Ltd. All rights reserved.

A comparative study of glycerol dehydration catalyzed by micro/mesoporous MFI zeolites

The catalytic properties of monomodal microporous and bimodal micro-mesoporous zeolites were investigated in the gas-phase dehydration of glycerol. The desilication methodology used to produce the mesoporous zeolites minimized diffusion limitations and increased glycerol conversion in the catalytic reaction due to the hierarchical system of secondary pores created in the zeolite crystals. The chemical and structural properties of the catalyst were studied by X-ray diffraction, nitrogen adsorption-desorption isotherms, NH3-TPD and pyridine chemisorption followed by IR-spectroscopy. Although the aim was to desilicate to create mesoporosity in the zeolite crystals, the desilication promoted the formation of extra-framework aluminum species that affected the conversion of glycerol and the products distribution. The results clearly show that the mesoporous zeolites with designed mesopore structure allowed a rapid diffusion and consequently improved the reaction kinetics. However, especial attention must be given to the desilication procedure because the severity of the treatment negatively interfered on the Brønsted and Lewis acid sites relative concentration and, consequently, in the efficiency of the catalysis performed by these materials. On the other hand, during the catalytic reaction, the intracrystalline mesopores allowed carbonaceous compounds to be deposited herein, resulting in less blocked micropores and catalysts with higher long-term stability.

The electro-oxidation of carbon monoxide and ethanol on supported Pt nanoparticles: The influence of the support and catalyst microstructure

The sluggish kinetics of ethanol oxidation on Pt-based electrodes is one of the major drawbacks to its use as a liquid fuel in direct ethanol fuel cells, and considerable efforts have been made to improve the reaction kinetics. Herein, we report an investigation on the effect of the Pt microstructure (well-dispersed versus agglomerated nanoparticles) and the catalyst support (carbon Vulcan, SnO2, and RuO2) on the rate of the electrochemical oxidation of ethanol and its major adsorbed intermediate, namely, carbon monoxide. By using several structural characterization techniques such as X-ray diffraction, X-ray absorption spectroscopy, and transmission electron microscopy, along with potentiodynamic and potentiostatic electrochemical experiments, we show that by altering both the Pt microstructure and the support, the rate of the electrochemical oxidation of ethanol can be improved up to a factor of 12 times compared to well-dispersed carbon-supported Pt nanoparticles. As a result of a combined effect, the interaction of Pt agglomerates with SnO2 yielded the highest current densities among all materials studied. The differences in the activity are discussed in terms of structural and electronic properties as well as by mass transport effects, providing valuable insights to the development of more active materials. © 2013 Springer-Verlag Berlin Heidelberg.

POPIN: a catalyst for a better international exchange of population information

Analiza las actividades del POPIN, cuyo objetivo es ayudar al establecimiento de nuevos servicios de información y coordinar el intercambio entre los existentes, compatibilizando las tareas para mejorar el flujo de información sobre población y la utilización de las fuentes disponibles. Incluye las recomendaciones de la Cuarta Reunión del POPIN realizada en Beijing entre el 22 y el 25 de octubre de 1986; y una lista descriptiva de sus publicaciones.

Shvo's catalyst in chemoenzymatic dynamic kinetic resolution of amines-inner or outer sphere mechanism?

Evidence is provided for the inner-sphere mechanism with actual metal coordination of the racemic amine in the crucial hydrogen transfer step promoted by Shvo's catalyst of the chemoenzymatic dynamic kinetic resolution (DKR) of amines. Key intermediates involved in this H-transfer step were intercepted and continuously monitored by electrospray ionization mass spectrometry (ESI-MS) and characterized by their dissociation chemistries via ESI-MS/MS. © 2013 The Royal Society of Chemistry.

Effect of the balance between Co(II) and Co(0) oxidation states on the catalytic activity of cobalt catalysts for Ethanol Steam Reforming

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Multivariate curve resolution analysis applied to time-resolved synchrotron X-ray Absorption Spectroscopy monitoring of the activation of copper alumina catalyst

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Sodium titanate as basic catalyst in transesterification reactions

Sodium titanate was synthesized by the sol-gel method and characterized using X-ray diffraction, thermogravimetry-mass spectrometry, atomic absorption spectroscopy, scanning electron microscopy, energy-dispersive X-ray analysis and nitrogen physisorption. The non-calcined material was active as a catalyst in transesterification reactions and showed high stability. An appreciable loss of activity on the fourth reuse was accompanied by the appearance of a new species of oxygen and segregated sodium, identified by X-ray photoelectron spectroscopy (XPS). The XPS spectrum showed that the basic nature of the framework oxygen was inferior to the original basicity, which explained the decline in catalytic activity. (C) 2013 Elsevier Ltd. All rights reserved.