Development of a heavy metal sorption system through the P=S functionalization of coconut (Cocos nucifera) fibers

Lignocellulosic residues are interesting materials for the production of heavy metal adsorbents for aquatic systems. Whole fibers taken from coconut (Cocos nucifera) husks were functionalized with the thiophosphoryl (P=S) group by means of the direct reaction with CI(3)P=S, (CH(3)O)(2)CIP=S or (CH(3)CH(2)O)(2)CIP=S in order to obtain an adsorptive system for `soft` metal ions, particularly Cd(2+). These functionalized fibers (FFs) were characterized by means of elemental analysis, infrared spectroscopy, thermal analysis and acid-base titration. Adsorption isotherms for Cd(2+) fitted the Langmuir model, with binding capacities of 0.2-5 mmol g(-1) of FF at 25 degrees C. (C) 2009 Elsevier Ltd. All rights reserved.

V(2)O(5) nanoparticles obtained from a synthetic bariandite-like vanadium oxide: Synthesis, characterization and electrochemical behavior in an ionic liquid

Highly stable and crystalline V(2)O(5) nanoparticles with an average diameter of 15 nm have been easily prepared by thermal treatment of a bariandite-like vanadium oxide, V(10)O(24)center dot 9H(2)O. Their characterization was carried out by powder X-ray diffractometry (XRD). Fourier transform infrared (FT-IR) and Raman spectroscopies, and transmission electron microscopy (TEM). The fibrous and nanostructured film obtained by electrophoretic deposition of the V(2)O(5) nanoparticles showed good electroactivity when submitted to cyclic voltammetry in an ionic liquid-based electrolyte. The use of this film for the preparation of a nanostructured electrode led to an improvement of about 50% in discharge capacity values when compared with similar electrodes obtained by casting of a V(2)O(5) xerogel. (C) 2009 Elsevier Inc. All rights reserved.

Electrostatic layer-by-layer deposition and electrochemical characterization of thin films composed of MnO(2) nanoparticles in a room-temperature ionic liquid

Thin films of MnO(2) nanoparticles were grown using the layer-by-layer method with poly (diallyldimetylammonium) as the intercalated layer. The film growth was followed by UV-vis, electrochemical quartz crystal microbalance (EQCM), and atomic force microscopy. Linear growth due to electrostatic immobilization of layers was observed up to 30 bilayers, but electrical connectivity was maintained only for 12 MnO(2)/PPDA bilayers. The electrochemical characterization of this film in 1-butyl-2,3-dimethyl-imidazolium (BMMI) bis(trifluoromethanesulfonyl)imide (TFSI) (BMMITFSI) with and without addition of a lithium salt indicated a higher electrochemical response of the nanostructured electrode in the lithium-containing electrolyte. On the basis of EQCM experiments, it was possible to confirm that the charge compensation process is achieved mainly by the TFSI anion at short times (<2 s) and by BMMI and lithium cations at longer times. The fact that large ions like TFSI and BMMI participate in the electroneutrality is attributed to the redox reaction that occurs at the superficial sites and to the high concentration of these species compared to that of lithium cations.

Removal of Zn(2+) from Electroplating Wastewater Using Modified Wood Sawdust and Sugarcane Bagasse

This paper describes the preparation of new adsorbents derived from sugarcane bagasse and wood sawdust (Manilkara sp.) to remove zinc (II) ions from electroplating wastewater. The first part deals with the chemical modification of sugarcane bagasse and wood sawdust, using succinic anhydride to introduce carboxylic acid functions into the material. The obtained materials (modified sugarcane bagasse MB2 and modified wood sawdust MS2) were then characterized by infrared spectroscopy (IR) and used in adsorption experiments. The adsorption experiments evaluates Zn(2+) removal from aqueous single metal solution and real electroplating wastewater on both batch and continuous experiments using fixed-bed columns prepared in laboratorial scale with the obtained adsorbents. Adsorption isotherms were then developed using Langmuir model and the Thomas kinetic model. The calculated Zn(2+) adsorption capacities were found to be 145 mg/g for MS2 and 125 mg/g for MB2 in single metal aqueous solution, whereas for the industrial wastewater these values were 61 mg/g for MS2 and 55 mg/g for MB2.

Characterization of Post-Consumer PET after Removal of the Original Surface: Influence of Raw Material

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

Metalização mecânica de ZrO2 com Ti para brasagem ZrO2/Aço com ligas de adição sem metal ativo

Metal/ceramic interfaces using zirconia have dominated the industrial applications in the last decade, due to the high mechanical strength and fracture toughness of zirconia, especially at temperatures below 300 ºC. Also noteworthy is the good ionic conductivity in high temperatures of this component. In this work joining between ZrO2 Y-TZP and ZrO2 Mg-PSZ with austenitic stainless steel was studied. These joints were brazed at high-vacuum after mechanical metallization with Ti using filler alloys composed by Ag-Cu and Ag-Cu-Ni. The influence of the metallization, and the affinity between the different groups (ceramic / filler alloys) was evaluated, in order to achieve strong metal/ceramic joints. Evaluation of joints and interfaces, also the characterization of base materials was implemented using various techniques, such as: x-ray diffraction, leak test, three-point flexural test and scanning electron microscopy with chemical analysis. The microstructural analysis revealed physical and chemical bonds in the metal/ceramic interfaces, providing superior leak proof joints and stress cracking, in order to a good joint in all brazed samples. Precipitation zones and reaction layers with eutetic characteristics were observed between the steel and the filler metal

Synthesis, characterization, and application of modified silica in the removal and preconcentration of lead ions from natural river water

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

Mechanism for interplay between electron and ionic fluxes in KhFek[Fe(CN)(6)](l)center dot mH(2)O compounds

This paper develops a framework for the interpretation of ionic insertion/deinsertion reactions in an aqueous environment taking place in transition-metal hexacyanoferrates of the general formula KhFek3+ [Fe2+ (CN)(6)](l)center dot mH(2)O, also called Prussian Blue. Three different processes were fully separated in the electrochemistry of these films. It was clearly identified that one of these electrochemical processes involves the insertion/deinsertion of H3O+ (hydrated protons) through the channels of the KhFek3+ [Fe2+ (CN)(6)](l) center dot mH(2)O structure to reach the film electroneutrality during the electron transfer between Everitt's Salt and Prussian Blue. The other electrochemical processes involve K+ or H+ (proton) exchange through the water crystalline structure existing in the channels of the KhFek3+ [Fe2+(CN)(6)](l)center dot mH(2)O structure.

Coloring ionic trapping states in WO3 and Nb2O5 electrochromic materials

Complex electro-optical analysis is a very useful approach to separate different kinetic processes that occur during ionic insertion reactions in electrochromic oxide materials. In this paper, we use this type of combined technique to investigate ionic and optical changes in different oxide host systems, i.e., in two oxide hosts, specifically WO3 and Nb2O5. A comparison of their electro-optical responses revealed the presence of an ionic trapping contribution to the kinetics of the coloring sites, which was named here as coloring ionic trapping state. As expected, this coloring trapping process is slower in Nb2O5 since the reduction potential of Nb2O5 is more negative (more energy is needed for a higher degree of coloration). A phenomenological solid-state model that encompasses homogeneous charge transfer and valence trapping was proposed to explain the coloring ionic trapping process. Basically the model is able to explain how ionic dynamics at low frequency region, i.e., the slower kinetic step, controls the coloring kinetics, i.e., how it is capable to regulate the coloring rates.Optical transient analyses demonstrated the possibility of the presence of more than one coloring ionic trap, indicating the complexity of the processes involved in coloration phenomenon in metal oxide host systems. (C) 2008 Published by Elsevier Ltd.

Dependence of divalent metal ions on phosphotransferase activity of osseous plate alkaline phosphatase

Kinetic evidence for the role of divalent metal ions in the phosphotransferase activity of polidocanol-solubilized alkaline phosphatase from osseous plate is reported. Ethylenediamine tetreacetate, 1,10-phenanthrolin, and Chelex-100 were used to prepare metal-depleted alkaline phosphatase. Except for Chelex-100, either irreversible inactivation of the enzyme or incomplete removal of metal ions occurred. After Chelex-100 treatment, full hydrolase activity of alkaline phosphatase was recovered upon addition of metal ions. on the other hand, only 20% of transferase activity was restored with 0.1 mu M ZnCl2, in the presence of 1.0 M diethanolamine as phosphate acceptor. In the presence of 0.1 mM MgCl2, the recovery of transferase activity increased to 63%. Independently of the phosphate acceptor used, the transferase activity of the metal-depleted alkaline phosphatase was fully restored by 8 mu M ZnCl2 plus 5 mM MgCl2. In the presence of diethanolamine as phosphate acceptor, manganese, cobalt, and calcium ions did nor stimulate the transferase activity. However, manganese and cobalt-enzyme catalyzed the transfer of phosphate to glycerol and glucose. (C) 1997 Elsevier B.V.

Mixed ionic-electronic YSZ/Ni composite for SOFC anodes with high electrical conductivity

The preparation of the ZrO(2):8 mol % Y(2)O(3)/NiO (YSZ/NiO) composites by a modified liquid mixture technique is reported. Nanometric NiO particles dispersed over the yttria-stabilized zirconia (YSZ) were prepared, resulting in dense sintered specimens with no solid solution formation between the oxides. Such a feature allowed for the electrical characterization of the composites in a wide range of relative volume fraction, temperature, and oxygen partial pressure. The main results indicate that the composites have high electrical conductivity, and the transport properties in these mixed ionic-electronic (MIEC) composites are strongly dependent on the relative volume fraction of the phases, microstructure, and temperature. These parameters should hence be taken into consideration for the optimized design of MIEC composites for electrochemical applications. In this context, the composite was reduced under H(2) for the preparation of high-conductivity YSZ/Ni cermets for use as solid oxide fuel cell anode material with relatively low metal content. (c) 2005 the Electrochemical Society. [DOI:10.1149/1.2149312] All rights reserved.

Study of an organically modified clay: Selective adsorption of heavy metal ions and voltammetric determination of mercury(II)

In this work, a hydrophilic clay, Na-montmorillonite from Wyoming, USA, was rendered organophilic by exchanging the inorganic interlayer cations for hexaclecyltrimethylammonium ions (HDTA), with the formulae of [(CH3)(3)N(C16H33)](+) ion. Based on fact that organo-clay has high affinities for non-ionic organic molecules, 1,3,4-thiadiazole-2,5-dithiol was loaded oil the HDTA-montmorillonite surface, resulting in the 1,3,4-thiadiazole-2,5-dithiol-HDTA-montmorillonite complex (TDD-organo-clay).The following properties of TDD-organo-clay are discussed: selective adsorption of heavy metal ions measured by batch and chromatographic column techniques, and utilization as preconcentration agent in a chemically modified carbon paste electrode (CMCPE) for determination of mercury(II).The main point of this paper is the construction of a selective sensor, a carbon paste electrode modified with TDD-organo-clay, its properties and its application to the determination of mercury(II) ions, as this element belongs to the most toxic metals. The chemical selectivity of this functional group and the selectivity of voltammetry were combined for preconcentration and determination. (c) 2005 Elsevier B.V. All rights reserved.

Multi-scale structural description of siloxane-PPO hybrid ionic conductors doped by sodium salts

Alkaline metal doped organic - inorganic hybrids have potential applications in the field of portable energy sources. Attractive sol - gel derived urea cross-linked polyether, siloxane - PPO ( poly( propylene oxide)) hybrids doped with sodium salts ( NaClO4 and NaBF4) were examined by multi-spectroscopic approach that includes complex impedance, X-ray powder diffraction (XRPD), small angle X-ray scattering (SAXS), Si-29 and Na-23 magic-angle spinning nuclear magnetic resonance (NMR/MAS), Na K-edge X-ray absorption near edge structure (XANES) and Raman spectroscopies. The goals of this work were to determine which cation coordinating site of the host matrix ( ether oxygen atoms or carbonyl oxygen atoms) is active in each of the materials analyzed, its influence on the nanostructure of the samples and its relation with the thermal and electrical properties. The main conclusion derived from this study is that the NaBF4 salt has a much lower solubility in the hybrid matrix than the NaClO4 salt. Furthermore, the addition of a large amount of salt plays a major role in the hybrid nanostructure and electrical properties, modifying the PPO chain conformation, weakening or breaking the hydrogen bond of the polyether - urea associations and changing the polycondensation and aggregation processes involving the siloxane species.

An evaluation into the potential of biological processing for the removal of metals from sewage sludges

The use of sewage sludge in agricultural land as a means of sludge disposal and recycling has been shown to be economical and suitable because of the presence of nutrients such as nitrogen and phosphorus. However, municipal sludges often contain high quantities of toxic metals and other compounds that must be removed for its safe use in agricultural soils. The biological leaching of metals from sewage sludges has been shown to be a promising technique for metal detoxifying in such complex matrix. The process efficiency is dependent on several physico-chemical parameters, such as total solids concentration, metal forms, pH-ORP, and temperature. Scale-up of the process has not yet been defined and is still pursuing the correct operational design. Current research involving the bioleaching of metals from sewage sludge and its application to land, which affects soil physical properties, are presented and discussed.

Langmuir-Blodgett films incorporating an ionic europium complex

Langmuir-Blodgett (LB) technique is a powerful tool to fabricate ultrathin films with highly ordered structures and controllable molecular array for efficient energy and electron transfer, allowing the construction of devices at molecular level. One method to obtain LB films consists in the mixture of classical film-forming molecules, for example Stearic Acid (SA) and functional metal complex. In this work NH(4)[Eu(bmdm)(4)], where the organic ligand bmdm is (butyl methoxy-dibenzoyl-methane) or (1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione) was used to build up Langmuir and LB films. Langmuir isotherms were obtained from (i) NH(4)[Eu(bmdm)(4)] complex and (ii) NH(4)[Eu(bmdm)(4)]/SA (1:1). Results indicated that (i) form multilayer structure; however the surface pressure was insufficient to obtain LB films, and (ii) can easily reproduce and build LB films. The dependence of number of layers in the UV absorption spectra suggest that the complex did not hydrolyze or show decomposition, UV spectral differences observed between the solution and the LB film indicate that the complex has a highly ordered arrangement in the film and the complex has an interaction with SA. Excitation spectra confirm a ligand-europium energy transfer mechanism. The transition lines of Eu(3+) ion were observed in emission spectra of all films, the photoluminescence spectra indicate a fluorescence enhanced effect with the number of LB layers. (C) 2009 Elsevier B.V. All rights reserved.