Silvio L.P. Dias

Pecan nutshell as biosorbent to remove Cu(II), Mn(II) and Pb(II) from aqueous solutions.

In the present study we reported for the first time the feasibility of pecan nutshell (PNS, Carya illinoensis) as an alternative biosorbent to remove Cu(II), Mn(II) and Pb(II) metallic ions from aqueous solutions. The ability of PNS to remove the metallic ions was investigated by using batch biosorption procedure. The effects such as, pH, biosorbent dosage on the adsorption capacities of PNS were studied. Four kinetic models were tested, being the adsorption kinetics better fitted to fractionary-order kinetic model. Besides that, the kinetic data were also fitted to intra-particle diffusion model, presenting three linear regions, indicating that the kinetics of adsorption should follow multiple sorption rates. The equilibrium data were fitted to Langmuir, Freundlich, Sips and Redlich-Peterson isotherm models. Taking into account a statistical error function, the data were best fitted to Sips isotherm model. The maximum biosorption capacities of PNS were 1.35, 1.78 and 0.946mmolg(-1) for Cu(II), Mn(II) and Pb(II), respectively.

Application of carbon adsorbents prepared from Brazilian-pine fruit shell for the removal of reactive orange 16 from aqueous solution: Kinetic, equilibrium, and thermodynamic studies.

Activated (AC-PW) and non-activated (C-PW) carbonaceous materials were prepared from the Brazilian-pine fruit shell (Araucaria angustifolia) and tested as adsorbents for the removal of reactive orange 16 dye (RO-16) from aqueous effluents. The effects of shaking time, adsorbent dosage and pH on the adsorption capacity were studied. RO-16 uptake was favorable at pH values ranging from 2.0 to 3.0 and from 2.0 to 7.0 for C-PW and AC-PW, respectively. The contact time required to obtain the equilibrium using C-PW and AC-PW as adsorbents was 5 and 4h at 298 K, respectively. The fractionary-order kinetic model provided the best fit to experimental data compared with other models. Equilibrium data were better fit to the Sips isotherm model using C-PW and AC-PW as adsorbents. The enthalpy and entropy of adsorption of RO-16 were obtained from adsorption experiments ranging from 298 to 323 K.

Metal Nanoparticle/Ionic Liquid/Cellulose: New Catalytically Active Membrane Materials for Hydrogenation Reactions

Transition metal-containing membrane films of 10, 20, and 40 μm thickness were obtained by the combination of irregularly shaped nanoparticles with monomodal size distributions of 4.8 ± 1.1 nm (Rh(0)) and 3.0 ± 0.4 nm (Pt(0)) dispersed in the ionic liquid (IL) 1-n-butyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide (BMI·(NTf)(2)) with a syrup of cellulose acetate (CA) in acetone. The Rh(0) and Pt(0) metal concentration increased proportionally with increases in film thickness up to 20 μm, and then the material became metal saturated. The presence of small and stable Rh(0) or Pt(0) nanoparticles induced an augmentation in the CA/IL film surface areas. The augmentation of the IL content resulted in an increase of elasticity and decrease in tenacity and toughness, whereas the stress at break was not influenced. The introduction of IL probably causes an increase in the separation between the cellulose macromolecules that results in a higher flexibility, lower viscosity, and better formability of the cellulose material. The nanoparticle/IL/CA combinations exhibit an excellent synergistic effect that enhances the activity and durability of the catalyst for the hydrogenation of cyclohexene. The nanoparticle/IL/cellulose acetate film membranes display higher catalytic activity (up to 7353 h(-1) for the 20 μm film of CA/IL/Pt(0)) and stability than the nanoparticles dispersed only in the IL.

Aspergillus terreus CCT 3320 immobilized on chrysotile or cellulose/TiO2 for sulfide oxidation

Abstract The increasing interest in applying chiral sulfoxides in asymmetric syntheses requires their preparation on a large scale, which can be obtained by enantioselective enzymatic oxidation of sulfides. We have focused on the preparation of sulfoxides 1 – 6 using Aspergillus terreus CCT 3320 cells to oxidize the precursor sulfides. These biotransformations lead to enantiomeric excesses (ee) better than 95%. In order to improve the biocatalytic process, the cells were immobilized on two supports, chrysotile and on cellulose/TiO 2 . The immobilized cells showed a similar biocatalytic behavior in the conversion rate and in the sulfoxide enantiomeric excess. Scanning electron microscopy (SEM) micrographs show that the cells are intertwined with the fibers of both supports, allowing fast separation from the reaction media and easing the biocatalyst reuse. Supported cells stored for at least 3 months showed no loss of activity.

Methylene blue immobilized on cellulose acetate with titanium dioxide: an application as sensor for ascorbic acid

. The electrode response was very fast, with an elapsed time of about 1.0 s, showing the potentiality to be utilized as an electrochemical sensor for determination of ascorbic acid in commercial samples.

Methylene blue immobilized on cellulose surfaces modified with titanium dioxide and titanium phosphate: factorial design optimization of redox properties

The electrochemical properties of methylene blue immobilized on cellulose surfaces modified with titanium dioxide and titanium phosphate were investigated by cyclic voltammetry. The materials synthesized were incorporated into carbon paste electrodes. The electron mediator property of the methylene blue was optimized using a factorial design, consisting of two levels and three factors. The factorial analysis was carried out by searching for better reversibility of the redox process, i.e. the lowest separation between positive and negative peak potentials and a current ratio near unity. The pH does not appear to influence the reversibility of electron transfer but electrolyte concentration and type of modified cellulose surface are important for this chemically modified electrode system. The experimental observations and data analyses indicate that a 0.5 mol l−1 NaCl solution and the cellulose surface modified with titanium phosphate at either a pH of 4.0 or 7.0 are optimal conditions for this system.

Cobalt(II) hematoporphyrin IX and protoporphyrin IX complexes immobilized on highly dispersed titanium(IV) oxide on a cellulose microfiber surface: electrochemical properties and dissolved oxygen reduction study

Hematoporphyrin IX (8,13-bis(1-hydroxyethyl)-3,7,12,17-tetramethyl-21H-23H-porphine-2,18-dipropionic acid) and protoporphyrin IX (8,13-divinyl-3,7,12,17-tetramethyl-21H-23H-porphine-2,18-dipropionic acid) were efficiently immobilized on a cellulose/titanium (IV) oxide composite fiber surface by the reaction of the porphyrin COOH groups with TiO2, presumably by forming the COOTi chemical bond. Furthermore, Co(II) was incorporated into the porphyrin ring, with this reaction being followed by UV–vis spectra in the solid state and confirmed by the change of the absorption bands due to a local symmetry change from D2h to D4h upon metallation of the porphyrin ring. Electrochemical studies by using cyclic voltammetry and chronoamperometry techniques, showed that the immobilized complexes catalyzed O2 reduction at −0.18 V for hematoporphyrin and −0.20 V for protoporphyrin in 1 mol l−1 KCl solution at pH 6. The cathodic current peak intensities plotted against O2 concentrations in the range from 0.5 to 13 mg l−1, showed a linear correlation. Rotating disk experiments were carried out in order to estimate the number of electrons involved on the process. It was observed that for both modified electrodes, dissolved O2 was reduced to H2O2 in a two-electron process.

Effects of first-row transition metals and impregnation ratios on the physicochemical properties of microwave-assisted activated carbons from wood biomass

First-row transition metals (Co, Ni, Cu and Zn) were successfully used in the preparation of activated carbons from wood biomass via microwave-assisted irradiation. Physical-chemical properties of the produced materials (MWAC) were studied by nitrogen adsorption-desorption curves, SEM, FTIR, UV-vis DRS and synchronous fluorescence spectroscopy, CHN elemental analysis, TGA/DTG, pHzpc, hydrophobic properties, and total acidity and basicity groups. Results showed that the metals were bound successfully in different amounts with surface functional groups of the wood biomass through ion exchange and surface complexation interaction during the impregnation step. Zn2+ and Cu2+ formed the most complexes. MWAC impregnated with Zn2+ showed higher pore volumes and surface areas, followed by Cu2+, Co2+ and Ni2+, independently of the ratio used. As the metal : biomass ratio was increased from 0.5 to 2, the surface area of MWAC increased from 300 to 620m2g-1 for Co-MC, 260 to 381m2g-1 for Ni-MC, 449 to 765m2g-1 for Cu-MC and from 572 to 1780m2g-1 for Zn-MC. The samples showed high values of carbon contents and oxygen-containing groups. An adsorption experiment revealed that samples prepared using ZnCl2 showed the highest sorption capacities (qe) for the tested adsorbates, followed by CuCl2, CoCl2 and NiCl2. These results matched with the surface areas and pore volumes trends, which were found to follow atomic number and melting point trends-Ni(II)bisphenol A>hydroquinone>4-nitro phenol>2-naphtol>paracetamol>caffeine>resorcinol.

Silica-alumina-niobia (SiO2/Al2O3/Nb2O5) matrix obtained by the sol-gel processing method: new material for online extraction of zinc ions

In the present work, a new material, SiO2/Al2O3/Nb2O5 (designated as SiAlNb), was evaluated as an adsorbent in a flow injection spectrophotometric method for online preconcentration and determination of trace amounts of Zn2+ ions. The preconcentration method is based on Zn2+ adsorption onto the surface of SiAlNb in alkaline medium (pH 9.0). The elution step is carried out using HNO3 solution, followed by reaction of the Zn2+ ions with 1-(2-piridylazo)-2-naphtol (pan) in ammoniacal buffer solution (pH 9.3) containing Tween-80. The [Zn(pan)2] complex formed is determined at 560 nm. The method presented a linear range between 7.6 and 180.0 µg L-1 (r = 0.9992) and limits of detection and quantification of 2.3 and 7.6 µg L-1, respectively. According to the Langmuir linear model, the maximum adsorption capacity was found to be 7.0 mg of Zn2+ g-1 of SiAlNb. The proposed method was successfully applied to the Zn2+ determination in water samples (lake, mineral, tap) and certified reference material (TORT-2 Lobster Hepatopancreas).

Electrochemical study and complete factorial design of Toluidine Blue immobilized on SiO2/Sb2O3 binary oxide

SiO2/Sb2O3 of specific surface area SBET = 788 m2 g−1 and 4.7 wt % of Sb was prepared by the sol–gel method. Toluidine Blue (TB+) was immobilized on SiO2/Sb2O3 by ion exchange reactions and the amount of dye bonded to the substrate surface was 13.72 μmol g−1 for SiO2/Sb2O3. This material was used to modify carbon paste electrodes and the electrochemical properties of Toluidine Blue (TB+) immobilized on a silica surface modified with antimonium trioxide were investigated by cyclic voltammetry. The electron mediator property of toluidine blue was optimized using a factorial design, consisting of four factors each at two levels. Factorial analysis was carried out by searching for better reversibility of the redox process, that is, the lowest separation between anodic and cathodic peak potentials and a current ratio near unity. The aqueous phase pH does not appear to influence the peak separation, ΔE, and the |Ipa//Ipc| current ratio response. The other factors studied, the scan rate, type of electrolyte and electrolyte concentration are important for this chemically modified electrode system demonstrating significant influences on the reversibility of electron transfer. The experimental observations and data analyses on this system indicate that the smallest peak separation occurs using 20 mV s−1 and 1.0 mol L−1 KCl while values of |Ipa//Ipc| close to unity are found for 20 mV s−1 with 1.0 mol L−1 concentrations of either KCl or CH3COONa. The electrodes presented reproducible responses and were chemically stable for various oxidation-reduction cycles.